CN104449760A

CN104449760A - Liquid crystal medium

Info

Publication number: CN104449760A
Application number: CN201410454006.6A
Authority: CN
Inventors: E·巴龙; J·福格特; 童琼; S·德罗
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2013-09-12
Filing date: 2014-09-09
Publication date: 2015-03-25
Anticipated expiration: 2034-09-09
Also published as: CN104449760B; EP2848676A2; KR20150030612A; JP2015054971A; US9487702B2; EP2848676A3; KR102223235B1; US20150070609A1; EP2848676B1; TWI643940B; JP6618678B2; TW201522586A

Abstract

The present invention relates to a liquid crystal (LC) medium comprising a polymerisable compound, as well as to a process for its preparation, to its use for optical, electro-optical and electronic purposes, in particular in an LC display, especially in an LC display of the PSA ('polymer sustained alignment') type, and to an LC display comprising it.

Description

Liquid crystal media

Technical field

The present invention relates to liquid crystal (LC) medium comprising polymerizable compound, prepare its method, it is for the purposes of optics, photoelectricity and electronics object, particularly be used in LC indicating meter, the purposes be particularly used in the LC indicating meter of PSA (" polymer-stabilized alignment ") type, and relate to the LC indicating meter comprising it.

Background technology

Those of the liquid-crystal display (LC indicating meter) of current use mainly TN (twisted-nematic) type.But these have the defect of striking contrast degree view angle dependency.

In addition, known so-called VA (" vertical orientation ") indicating meter has wider visual angle.The LC box of VA indicating meter is containing LC medium layer between two transparency electrodes, and wherein this LC medium often has negative dielectric (DC) anisotropy value.In the power-off state, the molecule of LC layer is perpendicular to electrode surface (vertically) or the vertically orientation that tilts.When being applied to by voltage on two electrodes, the orientation again that LC molecule is parallel to electrode surface can be there is.

In addition, known OCB (" optical compensation curved ") indicating meter, it is based on birefringence effect and have and have so-called " bending " orientation and usually positive (DC) anisotropic LC layer.When applying voltage, there is the again orientation of liquid crystal molecule perpendicular to electrode surface.In addition, OCB indicating meter comprises one or more Birefringent optical phase shift films usually, to prevent the less desirable photopermeability bending box in the dark state.OCB indicating meter has wider visual angle and shorter time of response relative to TN indicating meter.

It is also known that so-called IPS (" in face switch ") indicating meter, it is included in the LC layer between two substrates, and wherein to be only arranged in two substrates one upper and preferably have comb shaped structure interlaced with each other for two electrodes.Time thus to electrode application voltage, produce the electric field with the remarkable component being parallel to LC layer between which.This causes the orientation again in aspect of LC molecule.

In addition, also proposed so-called FFS (" fringing field switching ") indicating meter (especially see people such as S.H.Jung, Jpn.J.Appl.Phys., the 43rd volume, 3rd phase, 2004,1028), it comprises two electrodes equally on the same substrate, but, different from IPS indicating meter, wherein only have one and be structured as the form of electrode in the mode of comb shape, and another electrode is non-structured.Produce thus strong so-called " fringing field ", i.e. adjacent electrode edge place and highfield among whole box, this electric field produces has strong vertical component and strong horizontal component simultaneously.Both IPS indicating meter and FFS indicating meter all have very little contrast gradient view angle dependency.

In VA indicating meter more recently, the homogeneous orientation of LC molecule to be confined in LC box on multiple less farmland.Can exist to mistake between these farmlands, also referred to as tilt domain.There is the VA indicating meter of tilt domain, relative to traditional VA indicating meter, there is the visual angle not dependency of larger contrast gradient and gray scale.In addition, such indicating meter is more easily prepared, because no longer need the additional electrode surface treatment (such as by friction) for making the homogeneous orientation of molecule in an on state.Alternatively, the preferential sensing of pitch angle or tilt angle is controlled by the particular design of electrode.

In so-called MVA (" multi-zone vertical alignment nematic ") indicating meter, this point usually realizes by making electrode have to cause the projection of local pre-tilt.Thus, in different, specific box region, LC molecule is made to be parallel to electrode surface orientation when applying voltage in different directions.Realize " controlled " thus to switch, and prevent interfering formation to wrong line.Although this arrangement improves the visual angle of indicating meter, it causes the reduction of its light transmission.The further improvement of MVA employs the projection only on an electrode side, and opposed electrode has otch, which improves light transmission.The electrode of this otch produces uneven electric field when applying voltage in LC box, means and still achieves controlled switching.For improving light transmission further, the spacing between otch and projection can be expanded, but this causes again the prolongation of time of response.In so-called PVA (" patterning VA ") indicating meter, need not projection also feasible, because two electrodes carry out structurizing by otch on opposite side, this causes the light transmission of contrast gradient and the improvement of increasing, but this is difficulty technically and makes indicating meter more responsive to mechanical influence (" beating " etc.).Such as, but for many application, watch-dog and especially TV-screen, expect contrast gradient and the brightness (transmissivity) shortening the time of response and improve indicating meter.

Another kind of development is so-called PS (" polymer stabilizing ") or PSA (" polymer-stabilized alignment ") indicating meter, sometimes also uses term " polymer " stabilization to it ".Wherein, by one or more polymerizable compounds of a small amount of (such as 0.3 % by weight, typically <1 % by weight), preferred polymerisable monomer compound adds in LC medium, and be to apply voltage between electrode or under not executing alive situation, make its in-situ polymerization or crosslinked (usually by UV photopolymerization) after being filled with LC box.Be aggregated under LC medium demonstrates the temperature of mesomorphic phase and carry out, usually at room temperature carry out.Confirm polymerisable mesomorphic or liquid crystalline cpd (being also called reactive mesogen " RM ") to add in liquid crystal compound to be suitable for especially.

Except as otherwise noted, term " PSA " is below used to represent PS indicating meter and PSA indicating meter.

Meanwhile, PS (A) principle is just being used in various traditional LC indicating meter.Therefore, example has PSA-VA, PSA-OCB, PSA-IPS, PSA-FFS and PSA-TN-indicating meter as is known.When PSA-VA and PSA-OCB indicating meter, the polymerization of polymerizable compound (one or more) is preferably carried out under applying voltage, and when PSA-IPS indicating meter, being aggregated in of polymerizable compound applies or does not apply voltage, preferably carries out not executing in alive situation.As can be confirmed in testing cassete, PS (A) method causes the pre-tilt in box.When PSA-OCB indicating meter, such as warp architecture can be stabilized, thus make bias voltage be unnecessary or bias voltage can be reduced.With regard to the situation of PSA-VA-indicating meter, this pre-tilt has positive effect to the time of response.For PSA-VA indicating meter, standard MVA or PVA pixel and electrode lay-out can be used.But in addition, such as also such as only may use a structurized electrode side and not use projection to manipulate, this considerably simplifies preparation, and obtain splendid contrast gradient simultaneously, and have also obtained splendid light transmission simultaneously.

In addition, so-called positivity-VA indicating meter (" positivity VA ") has proved specially suitable pattern.Similar with traditional VA indicating meter, under original state time in positivity-VA indicating meter at no-voltage time, the initial orientation of LC molecule is a vertical plane, is namely substantially perpendicular to substrate.But, compared with traditional VA indicating meter, in positivity-VA indicating meter, employ the LC medium with positive dielectric anisotrop.Be similar in normally used IPS indicating meter, two electrodes in positivity-VA indicating meter are only arranged in two pieces of substrates, and preferably have interlaced and pectination (interdigital) structure.By applying voltage to interdigitated electrodes, which creating and being arranged essentially parallel to the parallel electric field of LC medium layer, by LC molecular conversion be substantially with the orientation of substrate-parallel.Also the stabilization (PSA) having proved polymkeric substance in positivity-VA indicating meter is favourable, and add in LC medium by RM, they are polymerized in box, can realize the remarkable shortening of switching time thus.

PSA-VA-indicating meter such as at JP 10-036847 A, EP 1 170 626 A2, US6,861,107, US 7,169,449, to be described in US2004/0191428 A1, US2006/0066793 A1 and US 2006/0103804 A1.PSA-OCB indicating meter is such as at T.-J-Chen etc., Jpn.J.Appl.Phys.45, and 2006,2702-2704 and S.H.Kim, L.-C-Chien, Jpn.J.Appl.Phys.43, be described in 2004,7643-7647.PSA-IPS indicating meter such as at US 6,177,972 and Appl.Phys.Lett.1999,75 (21), be described in 3264.PSA-TN indicating meter such as at Optics Express 2004,12 (7), be described in 1221.

Conventional LCD device described above is the same, and PSA indicating meter can operate as active matrix or passive matrix display.With regard to the situation of Active Matrix Display, each pixel usually by integrated non-linear active element as transistor (such as thin film transistor or " TFT ") carries out addressing, and with regard to the situation of passive matrix display, each pixel carries out addressing according to multiple transmission method as be known in the art usually.

PSA indicating meter one or two substrate in the substrate forming indicating meter box can also comprise both alignment layers, wherein said both alignment layers and LC medium contact and introduce the initial orientation of LC molecule, and wherein said both alignment layers is obtained by light orientation.

Especially in order to monitor and particularly in TV application, continue the optimization needing the time of response, and the optimization of the contrast gradient of LC indicating meter and brightness (also having transmissivity thus).PSA method can provide vital advantage here.Particularly in PSA-VA, PSA-IPS, PSA-FFS and PSA-positivity-VA indicating meter, the shortening of the time of response relevant to pre-tilt measurable in testing cassete can not have other parameters to obtain in obvious counteractive situation.

In prior art, such as, prepare the polymerizable compound of following formula:

Wherein P represents polymerizable groups, and it is normally acrylate-based or methacrylate based, such as, as US 7, and 169, as described in 449.

But, produced problem is that the not all combination be made up of LC mixture (also referring to below " LC body mixture ")+polymerizable components (usually RM) is all applicable to PSA indicating meter, because such as can not set up inclination maybe can not set up sufficient inclination at all, or such as because so-called " voltage keeps ratio " (VHR or HR) is inadequate concerning TFT display application.In addition, also find when being used in PSA indicating meter, the LC mixture known from prior art and RM still have some shortcomings.Therefore, not that the RM of each the known LC of dissolving in mixture is suitable in PSA indicating meter.In addition, except directly measuring in PSA indicating meter except volume pre-tilt, RM is difficult to find suitable choice criteria usually.If the mode of expecting not added by UV light light trigger carries out being polymerized (this is favourable for some application), then the selection being applicable to RM becomes even less.

In addition, the combination of the liquid crystal host mixture/RM of selection should have alap rotary viscosity and electrical property as well as possible.Particularly it should have VHR high as far as possible.In PSA indicating meter, especially need, with the high VHR after UV photoirradiation, because UV exposure is requisite part in indicating meter production process, but also to occur as normal exposure at the indicating meter run duration made.

Special desirably the obtainable type material of the pre-tilting angle providing generation little especially for PSA indicating meter.At this, preferred material can produce the pre-tilting angle lower than hitherto known material between polymerization period under the identical time shutter, even if and/or by use they also can realize after the shorter time shutter with known material obtainable (higher) pre-tilt angle.Thus, the production time (" pitch time ") of indicating meter can shorten and production technique one-tenth instinct reduce.

Another problem of producing in PSA indicating meter is existence or the removal of the unpolymerized RM of residual volume, particularly after the polymerization procedure for producing pre-tilt angle in the display.Such as, this kind of not reacted RM can affect the character of indicating meter negatively by being such as polymerized in uncontrollable mode during operation after indicating meter is made.

Therefore, the known PSA indicating meter of prior art often demonstrates the undesirable effect of what is called " image viscous (image sticking) " or " image burns ", after the electric field of image even in these pixels namely produced by the of short duration addressing of each pixel in LC indicating meter is disconnected or remain visible after the addressing of other pixel.

If use the LC body mixture with low VHR, then may occur this " image viscous " on the one hand.The UV-composition of daylight or back lighting may cause the decomposition reaction undesirably of wherein LC molecule and cause the generation of ion or free radical impurity thus.These may be accumulated, and particularly on electrode or both alignment layers, and they can reduce the voltage effectively applied there.This effect can also be observed in the traditional LC indicating meter not having polymeric constituent.

In addition, extra " image viscous " effect caused owing to there is unpolymerized RM is observed in PSA indicating meter of being everlasting.Remaining RM not controlled be aggregated in this by from environment UV light or caused by back lighting.In the display area connected, after multiple addressing period, this changes pitch angle.As a result, may occur that transmissivity changes in the region connected, and it remains unchanged in the region of access failure.

Therefore, it is desirable that, carry out as far as possible completely in the polymerization of PSA indicating meter production period RM and get rid of the existence that is not polymerized RM in the display as far as possible or be reduced to minimum value.For this reason, the material that can highly effectively and completely be polymerized is needed.Further, it is expected that the controlled reaction of these residual volumes.If than hitherto known material sooner and be more effectively polymerized, then this will be simpler to RM.

Another problem that will solve is that the RM of prior art has high fusing point usually, and only demonstrates limited solvability in many existing common LC mixtures, and therefore it often tends to spontaneous crystallizing out from mixture.In addition, the risk of auto-polymerization hinders LC body mixture and warms to dissolve polymerizable components, this means the solvability even at room temperature also needing maximum possible.In addition, such as also there is the risk of separation when being incorporated into by LC medium in LC indicating meter (chromatogram effect), this have impact on the homogeneity of indicating meter widely.This is by usually introducing LC medium at low temperatures to reduce the fact of the risk (see more than) of autohemagglutination and to increase further, and this has adverse influence to solvability conversely.

Another problem observed in prior art is the LC medium for PSA indicating meter, includes but not limited to the indicating meter of PSA type, usually shows high viscosity, and therefore shows high switching time.In order to reduce viscosity and the switching time of LC medium, prior art has advised adding thiazolinyl in LC compound.But, observe the reduction that the LC medium comprising alkenyl compound demonstrates reliability and stability usually, and be particularly exposed to the reduction of VHR after UV irradiates.Particularly for for during PSA indicating meter, this is quite disadvantageous, because the photopolymerization of RM is undertaken by being exposed to UV and irradiating usually in PSA indicating meter, this can cause again the reduction of VHR in LC medium.

Therefore, to PSA indicating meter, the particularly indicating meter of VA and OCB type, and there is great demand for the LC medium of such indicating meter and polymerizable compound, it does not show above-described shortcoming or only to show in little degree and it has the character of improvement.Especially, to PSA indicating meter, and all there is great demand for the material of PSA indicating meter, it makes it possible to have high resistivity, there is large operating temperature range, short time of response simultaneously, even at low temperatures, and there is low threshold voltage, low pre-tilt angle, the diversity of gray scale, high-contrast and wide visual angle, also there is the value of high " voltage keeps ratio " (VHR) after uv exposure, and there is low fusing point and solvability high in LC body mixture.

The object of the present invention is to provide the new material be applicable to for PSA indicating meter, particularly comprise RM and the LC medium of this material, its do not have above-described shortcoming or to the greatest extent with little degree there is above-mentioned shortcoming, can as far as possible fast and be fully polymerized, make it possible to reduce as quickly as possible set up pre-tilt angle, reduce or stop the generation of " image viscous " in indicating meter, and preferably make it possible to that there is very high resistivity value simultaneously, high VHR value, low threshold voltage and short time of response, and in the LC medium of body mixture in the common PSA of being used in indicating meter, there is high solvability.

Other objects of the present invention are to provide new RM, especially for optics, photoelectricity and electronic application, and the suitable method that present invention also offers for the preparation of it and intermediate.

Especially, the object of the present invention is to provide polymerizable compound, this compound creates larger maximum pre-tilt after photopolymerisation, this causes obtaining more quickly the pre-tilt of expectation and therefore creates time of the preparation LC indicating meter obviously shortened, and it can be easy to process in LC mixture.

This object is achieved by the materials and methods described in the application according to the present invention.Especially, have been found that in PSA indicating meter, use the multiple reactionness polymerizable compound of formula I hereinafter described to contribute to rapid polymerization reaction, the quick foundation at pitch angle expected and the low VHR value of LC medium after UV photopolymerization.It has also been found that, when using the multiple reactionness compound of formula I in the LC medium of compound comprising thiazolinyl, astoundingly reliability after uv exposure and VHR value with there is alkenyl compound compare higher with the LC medium of double reactive polymerizable compound.

In addition, having been found that the multiple reactionness compound (it is included in the spacer groups between at least one polymerizable groups and aromatic kernel) by using formula I, polymerization rate can be improved further and reducing in mixture the residual volume not being polymerized RM.

Therefore, the multiple reactionness polymerizable compound with one or more spacer groups of use formula I allows kit containing the advantage of the LC body mixture of thiazolinyl as the viscosity reduced and switching time faster, avoids the shortcoming of this body mixture as the reliability of reduction and low VHR value simultaneously.

Summary of the invention

The present invention relates to liquid crystal (LC) medium, it comprises the polymerizable compound of one or more following formula I, and also comprise one or more mesomorphic comprising thiazolinyl or liquid crystalline cpds, under the condition that wherein said thiazolinyl is preferably polymerized at the polymerizable compound for formula I, described polyreaction is stablized.

Wherein each group has following meanings

M is 0 or 1,

P ¹, P ², P ³represent polymerizable groups independently of one another,

Sp ¹, Sp ², Sp ³represent spacer groups or singly-bound, wherein Sp independently of one another ¹, Sp ²and Sp ³at least one be not singly-bound,

L represents P-Sp-, F, Cl, Br, I ,-CN ,-NO ₂,-NCO ,-NCS ,-OCN ,-SCN ,-C (=O) N (R ^x) ₂,-C (=O) Y ¹,-C (=O) R ^x,-N (R ^x) ₂, the optional silyl replaced, has aryl or the heteroaryl of the optional replacement of 5 to 20 annular atomses, or has 1 to 25, particularly preferably has the straight or branched alkyl of 1 to 10 C atom, in addition, and wherein one or more non-conterminous CH ₂group can separately independently of one another by-C (R ⁰⁰)=C (R ⁰⁰⁰)-,-C ≡ C-,-N (R ⁰⁰)-,-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-replace in the not direct interconnective mode of O and/or S atom, and in addition, wherein one or more H atom can be replaced by F, Cl, CN or P-Sp-,

R ⁰⁰and R ⁰⁰⁰the respective alkyl representing H independently of one another or there is 1 to 12 C atom,

R is 0,1,2 or 3,

R ^xrepresent P-Sp-, H, halogen, has the alkyl of the straight chain of 1 to 25 C atom, side chain or ring-type, wherein one or more non-conterminous CH ₂-group is optionally replaced in the not direct interconnective mode of O-and/or S-atom by-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-, and wherein one or more H atom are optionally replaced by F, Cl or P-Sp-, the aryl with 5 to 20 annular atomses of optional replacement, aryloxy, heteroaryl or heteroaryloxy

P has for P ¹one of implication provided,

Sp has for Sp ¹or Sp ²one of implication provided.

The invention still further relates to the purposes of described LC medium in LC indicating meter, the purposes preferably in the active layer or both alignment layers of LC indicating meter, wherein LC indicating meter is preferably PSA (polymer-stabilized alignment) type.

The invention still further relates to the LC medium comprising following component:

-polymerizable components A), it comprises one or more polymerizable compounds, and wherein at least one is the compound of formula I, and

-liquid crystal components B), it is hereafter also referred to as " LC body mixture ", this component comprises one or more, preferably two or more lower molecular weights (monomer and not polymerisable) compound, this compound is preferably selected from mesomorphic or liquid crystalline cpd, wherein at least one of these mesomorphics or liquid crystalline cpd comprises thiazolinyl, and wherein said thiazolinyl is preferably stablized polyreaction under for described polymerizable compound polymerizing condition.

The invention still further relates to as above LC medium hereinafter described, wherein said polymerizable compound or polymerizable components A) through polymerization.

The invention still further relates to the LC medium comprising polymkeric substance, described polymkeric substance is optionally polymerized with one or more other polymerizable compounds by the polymerizable compound of one or more formula I and obtains, or by polymerizable components A as above) polymerization obtain, and comprise one or more other compounds, this compound also can be mesomorphic, liquid crystal and/or polymerisable, or B component as above).

The invention still further relates to the method for preparation as above LC medium hereinafter described, it comprises the following steps: make as above one or more combinations of low molecular weight liquid crystals compounds hereinafter described or LC body mixture or liquid crystal components B), with the polymerizable compound of one or more formula I and optionally mix with other liquid crystalline cpds and/or additive.

The invention still further relates to the purposes in PSA indicating meter according to polymerizable compound of the present invention and LC medium, purposes particularly in the PSA indicating meter comprising LC medium, for producing the pitch angle in LC medium by polymerizable compound according to the present invention (preferably in an electrical or magnetic field) in-situ polymerization in PSA indicating meter.

The invention still further relates to and comprise one or more LC indicating meters, particularly PSA indicating meter according to polymerizable compound of the present invention or LC medium, be particularly preferably PSA-VA, PSA-OCB, PSA-IPS, PS-FFS, PSA-positivity-VA or PSA-TN indicating meter.

The invention still further relates to the polymerizable compound that comprises by being polymerized one or more formula I or polymerizable components A as above) polymkeric substance that obtains, or the LC indicating meter comprised according to LC medium of the present invention, particularly PSA indicating meter, is particularly preferably PSA-VA, PSA-OCB, PSA-IPS, PS-FFS, PSA-positivity-VA or PSA-TN indicating meter.

The invention still further relates to comprise and there are two substrates, two electrodes and substrate between the LC indicating meter of PSA type of LC box of LC medium layer, wherein at least one substrate is printing opacity and at least one substrate has one or two electrode, described LC medium comprise through polymerization component and lower-molecular-weight component, the wherein said component through polymerization is by the polymerization acquisition in LC medium between the substrate of LC box of one or more polymerizable compounds, preferably when being polymerized to during electrode application voltage, at least one wherein in polymerizable compound is selected from formula I, and/or wherein LC medium is as above LC medium hereinafter described.

The invention still further relates to the method for manufacture as above LC indicating meter hereinafter described, it comprises the following steps: will comprise as above one or more combinations of low molecular weight liquid crystals compounds hereinafter described or LC host compound or liquid crystal components B) LC medium and the as above polymerizable compound of one or more formula I hereinafter described or polymerizable components A) be filled in the LC box as above hereinafter described with two substrates and two electrodes; With polymerizing polymerizable compound, preferably being polymerized to during electrode application voltage.

PSA indicating meter according to the present invention has two electrodes, the form of its preferably transparent layer, is put in the substrate forming LC box on one or two.In each case: an electrode is applied to each in two substrates, such as, in PSA-VA, PSA-OCB or PSA-TN indicating meter according to the present invention; Or one that two electrodes is only applied in two substrates, and another substrate there is no electrode, such as, in PSA-positivity-VA according to the present invention, PSA-IPS or PSA-FFS indicating meter.

Term definition

As used herein, term " inclination " and " pitch angle " represent the inclination orientation of the LC molecule of LC medium relative to box surface in LC indicating meter (being preferably PSA indicating meter here).Here pitch angle represents the average angle (<90 °) between the surface of the vertical element axle (LC director) of LC molecule and the parallel planes external plates of formation LC box.Here the pitch angle (namely larger depart from 90 ° of angles) of lower value corresponds to larger inclination.The appropriate method for incline measurement is given in embodiment.Except as otherwise noted, tilt values disclosed in context relates to this measuring method.

The term " mesomorphic group " used in the present invention is well known by persons skilled in the art and is described in the literature, and represent that it contributes in fact in lower molecular weight or polymeric material, produce liquid crystal (LC) phase due to the interactional anisotropic group attracted and repel.Comprise the compound (mesomorphic compound) of mesomorphic group and not necessarily itself there is LC phase.For mesomorphic compound, only with other compound after and/or after polymerisation, also likely show LC phase behavior.Usual mesomorphic group is the little bar-shaped of such as rigidity or patelliform unit.Pure Appl.Chem.73 (5), 888 (2001) and C.Tschierske, G.Pelzl, S.Diele., Angew.Chem.2004, gives the summary of the term and definition used about mesomorphic or liquid crystal LC compound in 116,6340-6368.

Term " spacer groups " hereinafter also refers to " Sp ", it is known to those skilled in the art, and be described in the literature, for example, see Pure Appl.Chem.73 (5), 888 (2001) and C.Tschierske, G.Pelzl, S.Diele., Angew.Chem.2004,116,6340-6368.Just as used in the present invention, term " spacer groups " or " spacer " represent the flexible group connecting mesomorphic group and polymerizable groups in polymerizable mesomorphic compound, such as alkylidene group.

As used herein, term " reactive mesogen " and " RM " represent the compound comprising the functional group of a mesomorphic group and one or more applicable polymerization, and the functional group of described one or more applicable polymerization also refers to " polymerizable groups " or " P ".

As what hereinafter use, except as otherwise noted, term " polymerizable compound " represents polymerisable monomeric compound.

As what hereinafter use, except as otherwise noted, term " polymerisable " refers to and is containing group P or P ^1-3the condition that uses of compound polymerization under polymerisable, described compound is the as above compound such as formula I hereinafter described or polymerizable compound or RM.

As used herein, term " low-molecular weight compound " and " not polymerisable compound " represent the compound of normally monomer, and it containing under the applicable condition that those skilled in the art are usually known in the prior art, is not particularly containing group P or P ^1-3the compound functional group of being polymerized under as above polymerizable compound hereinafter described or RM are polymerized the condition used.

As used herein, term " active layer " and " switchable layer " represent in Electro-Optical Display, such as, layer in LC indicating meter, it comprises one or more and has structure and optically anisotropic molecule, such as LC molecule, it, when being subject to the outside stimulus as electric field or magnetic field, will change their orientation, and this causes this layer to the radioparent change of polarization or non-polarized light.

Contextual " organic group " represents carbon back or hydrocarbyl group.

" carbon back " represents the unit price or the multivalent organic group that comprise at least one carbon atom, wherein this group does not comprise other atoms (such as-C ≡ C-), or optionally comprise other atoms one or more, such as N, O, S, B, P, Si, Se, As, Te or Ge (such as carbonyl etc.).Term " hydrocarbyl group " expression additionally comprises one or more H atom and optionally comprises the carbon back of one or more heteroatoms such as N, O, S, B, P, Si, Se, As, Te or Ge.

" halogen " represents F, Cl, Br or I.

-CO-,-C (=O)-and-C (O)-expression carbonyl group, namely

" conjugated radicle " or " conjugation group " expression comprises sp in principle ²the base of-hydridization (or may be also sp-hydridization) carbon atom or group, it can also be replaced by corresponding heteroatoms.In the simplest situation, alternately there is double bond or singly-bound in this expression.In this connection, the defect causing conjugation to be interrupted that " in principle " expression nature (nonrandom) produces does not make term " conjugation " go bad.In addition, if when such as arylamine units or some heterocycle (namely by N, O, P or S atom conjugation) are positioned on base or group, term " conjugation " is same in the application.

Carbon back or alkyl can be saturated or unsaturated groups.Unsaturated group is such as aryl, alkenyl or alkynyl.Have more than the carbon back of 3 C atoms or alkyl can be straight chain, side chain and/or ring-type, and screw connection or fused rings can be comprised.

Term " alkyl ", " aryl ", " heteroaryl " etc. also comprise multivalence group, such as alkylidene group, arylidene, heteroarylidene etc.

The group that term " aryl " represents aromatic series carbon back or derived by it.Term " heteroaryl " represents and comprises one or more heteroatomic " aryl " defined above.

Preferred carbon back and hydrocarbyl group be optional replace there is 1 to 40, preferably there is 1 to 25, particularly preferably there is the alkyl of 1 to 18 C atom, thiazolinyl, alkynyl, alkoxyl group, alkyl-carbonyl, alkoxy carbonyl, alkyl carbonyl oxy and alkoxyl group carbonyl oxygen base, there are 6 to 40, preferably there is aryl or the aryloxy of the optional replacement of 6 to 25 C atoms, or there are 6 to 40, preferably there is the alkylaryl of the optional replacement of 6 to 25 C atoms, arylalkyl, alkyl-aryloxy, alkoxy aryl, aryl carbonyl, aryloxycarbonyl, aryl-carbonyl oxygen and aryloxy carbonyl oxygen base.

Other preferred carbon backs and alkyl are C ₁-C ₄₀alkyl, C ₂-C ₄₀thiazolinyl, C ₂-C ₄₀alkynyl, C ₃-C ₄₀allyl group, C ₄-C ₄₀alkane dialkylene (alkyldienyl), C ₄-C ₄₀polyene-based, C ₆-C ₄₀aryl, C ₆-C ₄₀alkylaryl, C ₆-C ₄₀arylalkyl, C ₆-C ₄₀alkyl-aryloxy, C ₆-C ₄₀alkoxy aryl, C ₂-C ₄₀heteroaryl, C ₄-C ₄₀cycloalkyl, C ₄-C ₄₀cycloalkenyl group etc.Particularly preferably be C ₁-C ₂₂alkyl, C ₂-C ₂₂thiazolinyl, C ₂-C ₂₂alkynyl, C ₃-C ₂₂allyl group, C ₄-C ₂₂alkane dialkylene, C ₆-C ₁₂aryl, C ₆-C ₂₀arylalkyl and C ₂-C ₂₀heteroaryl.

Other preferred carbon backs and alkyl be there is 1 to 40, preferably have the straight chain of 1 to 25 C atom, side chain or cyclic alkyl, it is unsubstituted or mono-or polysubstituted by F, Cl, Br, I or CN, wherein one or more non-conterminous CH ₂group can separately independently of one another by-C (R ^x)=C (R ^x)-,-C ≡ C-,-N (R ^x)-,-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-replace in the not direct interconnective mode of O and/or S atom.

R ^xpreferably represent H, halogen, there is the straight chain of 1 to 25 carbon atom, side chain or cyclic alkyl chain, in addition, wherein one or more non-conterminous C atoms also can be replaced by-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-, and wherein one or more H atom also can be replaced by fluoro, there is aryl or the aryloxy of the optional replacement of 6 to 40 C atoms, or there is the heteroaryl of optional replacement or the heteroaryloxy of 2 to 40 C atoms.

Preferred Alkoxy in this way methoxyl group, oxyethyl group, 2-methoxy ethoxy, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, 2-methylbutoxy group, n-pentyloxy, positive hexyloxy, positive heptan oxygen base, n-octyloxy, positive ninth of the ten Heavenly Stems oxygen base, n-decyloxy, n-undecane oxygen base, n-dodecane oxygen base etc.

Preferred alkyl is such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, 2-methyl butyl, n-pentyl, sec.-amyl sec-pentyl secondary amyl, cyclopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-heptyl, suberyl, n-octyl, ring octyl group, n-nonyl, positive decyl, n-undecane base, dodecyl, dodecyl (dodecanyl), trifluoromethyl, perfluoro-n-butyl group, 2,2,2-trifluoroethyl, perfluoro capryl, perfluoro hexyl etc.

Preferred thiazolinyl is such as vinyl (vinyl), vinyl (ethenyl), propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctene base etc.

Preferred alkynyl is such as ethynyl, proyl, butynyl, pentynyl, hexin base, octyne base etc.

Preferred amino is such as dimethylamino, methylamino, MethYlphenylamino, phenyl amino etc.

Preferred carbon back and alkyl are aryl and heteroaryl further, and it is preferably containing 3 to 20 annular atomses.Aryl and heteroaryl can be monocycles, and namely they can comprise a ring, or many rings, namely containing two or more rings.Polyaromatic or heteroaryl can contain the ring (such as xenyl) of condensed ring (such as naphthyl) or covalent bonding, or contain the ring of condensed ring and bonding.Heteroaryl contains one or more heteroatoms, is preferably selected from O, N, S and Se.

Particularly preferably be the list with 5 to 25 C atoms-, two-or three cyclophane bases and have the list of 3 to 25 annular atomses-, two-or tricyclic heteroaryl, it optionally comprises fused rings and is optionally replace.Further preferably 5-, 6-or 7-unit aryl and and heteroaryl, in addition, wherein one or more CH groups can be replaced with O atom and/or the not direct interconnective mode of S atom by N, S or O.

Preferred aryl be such as phenyl, xenyl, terphenyl, [1,1':3', 1 "] terphenyl-2 '-Ji, naphthyl, anthryl, binaphthylyl, phenanthryl, 9,10-Dihydro-phenanthrenyl, pyrene, dihydropyrene, perylene, tetracene, pentacene, benzopyrene, fluorenes, indenes, indenofluorene, spiral shell difluorene etc.

Preferred heteroaryl is such as 5-ring, such as pyrroles, pyrazoles, imidazoles, 1,2,3-triazoles, 1,2,4-triazole, tetrazolium, furans, thiophene, selenophen, oxazole, isoxazole, 1,2-thiazole, 1,3-thiazoles, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazoles, 1,2,4-thiadiazoles, 1,2,5-thiadiazoles, 1,3,4-thiadiazoles, 6-ring, such as pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazines, 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, or condensed group, such as indoles, isoindole, indolizine, indazole, benzoglyoxaline, benzotriazole, purine, naphtho-imidazoles, phenanthro-imidazoles, pyridine-imidazole, pyrazine imidazoles, quinoxaline imidazoles, benzoxazole, Nai Bing oxazole, En Bing oxazole, Fei Bing oxazole, isoxazole, benzothiazole, cumarone, isobenzofuran, diphenylene-oxide, quinoline, isoquinoline 99.9, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, benzisoquinoline, acridine, benzothiazine, benzoxazine, benzo pyridazine, benzo pyrimidine, quinoxaline, azophenlyene, naphthyridines, azepine carbazole, benzo carboline, phenanthridines, phenanthroline, thieno-[2,3b] thiophene, thieno-[3,2b] thiophene, two thienothiophenes, different thionaphthene, dibenzothiophene, diazosulfide thiophene, or the combination of these groups.

Above-mentioned aryl and heteroaryl can also be replaced by alkyl, alkoxyl group, alkylthio, fluorine, fluoro-alkyl or other aryl or heteroaryl groups.

Preferred carbon back and alkyl are non-aromatic carbocycle or heterocyclic group further, and it is preferably containing 3 to 20 annular atomses.Carbocyclic ring and heterocyclic group can contain saturated rings, the ring be namely only made up of singly-bound, and/or the undersaturated ring of part, the ring be namely made up of as double bond singly-bound and multiple bond.Heterocycle contains one or more heteroatoms, is preferably selected from Si, O, N, S and Se.

Non-aromatic carbocycle and heterocyclic group can be monocycles, namely only containing a ring, or many rings, namely containing two or more rings.The carbocyclic ring of many rings or heterocyclic group can contain condensed ring (such as in naphthane or dicyclo [2.2.1] octane), or the ring of covalent bonding (such as 1,1 '-bicyclohexane), or the ring of condensed ring and covalent bonding.

Particularly preferably be only containing non-aromatic carbocycle and the heterocyclic group of saturated rings.Further preferably have the list of 5 to 25 annular atomses-, two-or the non-aromatic carbocycle of three cyclic groups and heterocyclic group, it is optionally containing fused rings and be optionally be substituted.Again further preferably 5-, 6-, 7-or 8-unit carbon ring group, in addition, wherein one or more C atoms also can be replaced by Si and/or one or more CH group can be replaced by N and/or one or more non-conterminous CH ₂group can be replaced by-O-and/or-S-.

Preferred carbocyclic ring and heterocyclic group are such as 5 yuan of groups such as pentamethylene, tetrahydrofuran (THF), tetramethylene sulfide, tetramethyleneimine; 6 yuan of groups such as hexanaphthene, Silinane (silinane), tetrahydrobenzene, tetrahydropyrans, tetrahydric thiapyran, 1,3-bis-oxazole, 1,3-dithiane, piperidines; 7 yuan of groups such as suberane; With condensed group such as tetraline, naphthane, indane, dicyclo [1.1.1] pentane-1,3-bis-base, dicyclo [2.2.2] octane-Isosorbide-5-Nitrae-two base, spiral shell [3.3] heptane-2,6-bis-base, octahydro-4,7-endo-methylene group indane-2,5-bis-base.

Preferred substituting group is such as dissolve promotion property group, such as alkyl or alkoxyl group; Electron-withdrawing group, such as fluorine, nitro or nitrile; Or for improving the substituting group of glass transition temperature of polymer (Tg), particularly bulky group, the such as tertiary butyl or the optional aryl replaced.

Preferred substituting group, context is also called " L ", and such as it is F, Cl, Br, I ,-CN ,-NO ₂,-NCO ,-NCS ,-OCN ,-SCN ,-C (=O) N (R ^x) ₂,-C (=O) Y ¹,-C (=O) R ^x,-N (R ^x) ₂, wherein R ^xthere is above-mentioned implication, and Y ¹represent halogen, the silyl of optional replacement or there are 6 to 40, preferably there is the aryl of the optional replacement of 6 to 20 C atoms, and there is the alkyl of straight or branched of 1 to 25 C atom, alkoxyl group, alkyl-carbonyl, alkoxy carbonyl, alkyl carbonyl oxy or alkoxyl group carbonyl oxygen base, wherein one or more H atom can optionally be replaced by F or Cl.

" silyl of replacement or aryl " preferably represents by halogen ,-CN, R ⁰,-OR ⁰,-CO-R ⁰,-CO-O-R ⁰,-O-CO-R ⁰or-O-CO-O-R ⁰replace, wherein R ⁰there is above-mentioned implication.

Particularly preferred substituting group L is such as F, Cl, CN, NO ₂, CH ₃, C ₂h ₅, OCH ₃, OC ₂h ₅, COCH ₃, COC ₂h ₅, COOCH ₃, COOC ₂h ₅, CF ₃, OCF ₃, OCHF ₂, OC ₂f ₅, in addition also have phenyl.

be preferably wherein L has one of above shown implication.

Polymerizable groups (P, P ¹, P ², P ³) be the group being applicable to polyreaction (such as free radical or ionic chain polymerization, addition polymerization or polycondensation), or be applicable to the group of polymeranaloguous reaction (such as addition or condensation on main polymer chain).For the group for chain polymerization, particularly preferably be those that particularly comprise C=C double bond or-C ≡ C-, and for the group of ring-opening polymerization, such as, be oxetanyl or epoxy group(ing).

Preferred polymerizable groups is selected from following group: CH ₂=CW ¹-CO-O-, CH ₂=CW ¹-CO-, cH ₂=CW ²-(O) _k3-, CW ¹=CH-CO-(O) _k3-, CW ¹=CH-CO-NH-, CH ₂=CW ¹-CO-NH-, CH ₃-CH=CH-O-, (CH ₂=CH) ₂cH-OCO-, (CH ₂=CH-CH ₂) ₂cH-OCO-, (CH ₂=CH) ₂cH-O-, (CH ₂=CH-CH ₂) ₂n-, (CH ₂=CH-CH ₂) ₂n-CO-, HO-CW ²w ³-, HS-CW ²w ³-, HW ²n-, HO-CW ²w ³-NH-, CH ₂=CW ¹-CO-NH-, CH ₂=CH-(COO) _k1-Phe-(O) _k2-, CH ₂=CH-(CO) _k1-Phe-(O) _k2-, Phe-CH=CH-, HOOC-, OCN-and W ⁴w ⁵w ⁶si-, wherein W ¹represent H, F, Cl, CN, CF ₃, phenyl or there is the alkyl, particularly H, F, Cl or CH of 1 to 5 C atom ₃; W ²and W ³represent separately H independently of one another or there is the alkyl, particularly H of 1 to 5 C atom, methyl, ethyl or n-propyl; W ⁴, W ⁵and W ⁶represent Cl independently of one another separately, there is the oxa alkyl of 1 to 5 C atom or oxa-carbonylic alkyl; W ⁷and W ⁸the respective alkyl representing H, Cl independently of one another or there is 1 to 5 C atom; Phe represents Isosorbide-5-Nitrae-phenylene, and it is optionally replaced by one or more not polymerizable groups L as defined above; k ₁, k ₂and k ₃represent 0 or 1, k independently of one another separately ₃preferred expression 1; And k ₄represent the integer of 1 to 10.

Particularly preferred polymerizable groups is selected from following group: CH ₂=CW ¹-CO-O-, CH ₂=CW ¹-CO-, cH ₂=CW ²-O-, CH ₂=CW ²-, CW ₁=CH-CO-(O) _k3-, CW ¹=CH-CO-NH-, CH ₂=CW ¹-CO-NH-, (CH ₂=CH) ₂cH-OCO-, (CH ₂=CH-CH ₂) ₂cH-OCO-, (CH ₂=CH) ₂cH-O-, (CH ₂=CH-CH ₂) ₂n-, (CH ₂=CH-CH ₂) ₂n-CO-, CH ₂=CW ¹-CO-NH-, CH ₂=CH-(COO) _k1-Phe-(O) _k2-, CH ₂=CH-(CO) _k1-Phe-(O) _k2-, Phe-CH=CH-and W ⁴w ⁵w ⁶si-, wherein W ¹represent H, F, Cl, CN, CF ₃, phenyl or there is the alkyl, particularly H, F, Cl or CH of 1 to 5 C atom ₃; W ²and W ³represent separately H independently of one another or there is the alkyl, particularly H of 1 to 5 C atom, methyl, ethyl or n-propyl; W ⁴, W ⁵and W ⁶represent Cl independently of one another separately, there is the oxa alkyl of 1 to 5 C atom or oxa-carbonylic alkyl; W ⁷and W ⁸the respective alkyl representing H, Cl independently of one another or there is 1 to 5 C atom; Phe represents Isosorbide-5-Nitrae-phenylene; k ₁, k ₂and k ₃represent 0 or 1, k independently of one another separately ₃preferred expression 1; And k ₄represent the integer of 1 to 10.

Polymerizable groups is very particularly preferably selected from following group: CH ₂=CW ¹-CO-O-, particularly CH ₂=CH-CO-O-, CH ₂=C (CH ₃)-CO-O-and CH ₂=CF-CO-O-is further CH ₂=CH-O-, (CH ₂=CH) ₂cH-O-CO-, (CH ₂=CH) ₂cH-O-,

Polymerizable groups is very particularly preferably selected from vinyl, vinyloxy group, acrylate-based, methacrylate based, fluoro acrylic ester base, chloropropene perester radical, oxetanyl and epoxy group(ing) further, and particularly preferably represents acrylate-based, methacrylate based or oxetanyl.

Spacer groups Sp, Sp ¹, Sp ²and Sp ³be preferably selected from formula Sp'-X', wherein Sp' and polymerizable groups (to such an extent as to such as make group P-Sp-, P ¹-Sp ¹-or P ²-Sp ²-or P ³-Sp ³-be respectively formula P-Sp'-X' or P ^1/2/3-Sp'-X'-) connect, wherein Sp' and X' has following implication:

Sp' represents to have 1 to 20, the alkylidene group of the preferred straight or branched of 1 to 15 C atom, and it is optionally mono-or polysubstituted by F, Cl, Br, I, CN or P, and in addition, wherein one or more non-conterminous CH ₂group can separately independently of one another by-O-,-S-,-NH-,-N (R ⁰)-,-Si (R ⁰⁰r ⁰⁰⁰)-,-CO-,-CO-O-,-O-CO-,-O-CO-O-,-S-CO-,-CO-S-,-N (R ⁰⁰)-CO-O-,-O-CO-N (R ⁰⁰)-,-N (R ⁰⁰)-CO-N (R ⁰⁰the mode that)-,-CH=CH-or-C ≡ C-did not directly connect mutually with O and/or S atom replaces,

X' represents-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-,-CO-N (R ⁰⁰)-,-N (R ⁰⁰)-CO-,-N (R ⁰⁰)-CO-N (R ⁰⁰)-,-OCH ₂-,-CH ₂o-,-SCH ₂-,-CH ₂s-,-CF ₂o-,-OCF ₂-,-CF ₂s-,-SCF ₂-,-CF ₂cH ₂-,-CH ₂cF ₂-,-CF ₂cF ₂-,-CH=N-,-N=CH-,-N=N-,-CH=CR ⁰-,-CY ²=CY ³-,-C ≡ C-,-CH=CH-CO-O-,-O-CO-CH=CH-or singly-bound, if the ester group group (O-CO or CO-O) wherein in it and formula I adjoins, then X " represents singly-bound.

R ⁰⁰and R ⁰⁰⁰the respective alkyl representing H independently of one another or there is 1 to 12 C atom.

Y ²and Y ³represent H, F, Cl or CN independently of one another separately, and

P defined such as formula in I.

X' is preferably-O-,-S-,-CO-,-COO-,-OCO-,-O-COO-,-CO-NR ⁰-,-NR ⁰-CO-,-NR ⁰-CO-NR ⁰-or singly-bound, be very preferably-O-or singly-bound.

Preferred group Sp, Sp ¹, Sp ², Sp ³*-(CH is included but not limited to Sp'-X' ₂) _p1-, *-(CH ₂) _p2-O-(CH ₂) _p3-, *-(CH ₂) _p2-S-(CH ₂) _p3-, *-(CH ₂) _p2-NH-(CH ₂) _p3-, *-(CH ₂) _p1-O-, *-(CH ₂) _p1-CO-, *-(CH ₂) _p1-CO-O-, *-(CH ₂) _p1-O-CO-and

Wherein asterisk (*) represents and the connection of each described polymerizable groups, and p1 is the integer of 1 to 12, and preferably from 1 to 6, and p2 and p3 is the integer of 1 to 6 independently of one another, preferably 1,2 or 3.

The present invention's preferred embodiment relates to the compound of formula I, wherein spacer groups Sp, Sp ¹, Sp ²and Sp ³represent Sp'-X', wherein Sp' is selected from straight-chain alkyl-sub-as defined above.

Another preferred embodiment of the present invention relates to and comprises at least one group P-Sp-, P ¹-Sp ¹-, P ²-Sp ²-or P ³-Sp ³-the compound of formula I, wherein Sp, Sp ¹, Sp ²or Sp ³represent Sp'-X' respectively, wherein the branched alkylidene that replaced by group P as defined above (polymerizable groups of side chain) of Sp'.

Further preferably such formula I, wherein

-m is 0,

-m is 1,

-P, P ¹, P ²and P ³be selected from acrylate-based, methacrylate based and oxetanyl,

-Sp ¹singly-bound,

-Sp ¹singly-bound, and Sp ²and Sp ³not singly-bound,

-Sp ¹not singly-bound,

-Sp ¹not singly-bound, and Sp ²and Sp ³singly-bound,

-Sp ¹, Sp ²and Sp ³not singly-bound,

Only containing three polymerizable groups, (it is by the group P shown in formula I for the compound of-Shi I ¹, P ²and P ³represent),

-except three group P ¹, P ²and P ³outside, the compound of formula I does not contain other polymerizable groups any,

-L does not represent or does not contain polymerizable groups,

-L does not represent or does not contain group P-Sp-,

At least one phenyl ring in-Shi I is not P-Sp-and not polymerisable group L replaces, and be preferably selected from F, Cl ,-CN and have 1 to 25, the straight or branched alkyl of particularly preferably 1 to 10 C atom, in addition, wherein one or more non-conterminous CH ₂group is independently of one another by-C (R ⁰⁰)=C (R ⁰⁰⁰)-,-C ≡ C-,-N (R ⁰⁰)-,-O-, the mode that directly do not connect each other with O and/or S atom of-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-replaces, and in addition, wherein one or more H atom are replaced by F, Cl, Br, I or CN,

In-Shi I, at least one of phenyl ring is replaced by one or two fluorine atom.

The compound of preferred formula I is selected from following minor:

Wherein P ¹, P ², P ³, Sp ¹, Sp ², Sp ³, L and r have the implication provided in formula I, or as above one of preferred implication hereinafter described.

Particularly preferably be the compound of formula I1, I2 and I3.

The compound of formula I is very preferably selected from following minor:

Wherein P ¹, P ²and P ³one of preferred implication that there is the implication that provides in formula I or provide as context, it is identical or be differently-O-,-CO-O-,-O-CO-or singly-bound when X occurs at every turn, preferably-O-or singly-bound, m and n is 0,1,2,3,4,5 or 6 independently of one another, and one of m and n is not 0 in each formula.

The compound of preferred formula I is selected from following minor further:

The compound of minor I1-1-1 to I5-8-1 further preferably as listed above, wherein said methacrylate based group is replaced by acrylate group.

The compound of formula I and minor thereof can adopt method that is well known by persons skilled in the art and that describe in vitochemical classic or similar approach preparation, such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Thieme-Verlag, Stuttgart.The method of the suitable reactive reactive mesogen of preparation three is such as disclosed in US 8,313, in 669.

The compound of formula I such as can comprise polymerizable groups P or P by use ^1,2,3corresponding acid, acid derivative or corresponding intermediate is carried out esterification to halogenated compound or etherificate is synthesized, wherein polymerizable groups P and P ^1,2,3replaced by OH.

Shown in as exemplary in scheme 1, (wherein Phe represents phenylene, Sp for acrylate or methacrylic ester ^1,2,3with A, there is the above implication provided, and " Acr " represents acrylate-based or methacrylate based) can be prepared by corresponding alcohol and acid derivative (such as (methyl) acrylate chloride or (methyl) acrylic anhydride) esterification under the existence of alkali (such as pyridine or triethylamine and 4-(N, N-dimethylamino) pyridine (DMAP)).Or, ester can be prepared by alcohol and the esterification under the existence of dewatering agent of (methyl) vinylformic acid, such as, use dicyclohexylcarbodiimide (DCC), N-(3-dimethylaminopropyl)-N '-ethylcarbodiimide (EDC) or hydrochloric acid N-(3-dimethylaminopropyl)-N '-ethylcarbodiimide and DMAP according to Steglich.

scheme 1

HO-Sp ¹-Phe-A-Phe(Sp ²-OH)(Sp ³-OH)

↓

Acr-Sp ¹-Phe-A-Phe(Sp ²-Acr)(Sp ³-Acr)

Intermediate can according to or be similar to describe in document currently known methods synthesis.

The additive method of the compound and intermediate thereof of preparing above formula is exemplarily presented in following reaction scheme.

scheme 2

The compound of other formula I can be prepared according to method similar to the above.

For the preparation of PSA indicating meter, polymerizable compound carries out in-situ polymerization to be polymerized or crosslinked (if a kind of compound comprises two or more polymerizable groups) by applying voltage in LC medium between the substrate of LC indicating meter.Polymerization can be carried out in a step.First can also apply in a first step voltage to carry out being polymerized to produce pre-tilt angle, and afterwards, not execute in alive second polymerization procedure, be polymerized or unreacted compound (" finally solidifying ") in the crosslinked the first step.

Suitable and preferred polymerization process is such as thermopolymerization or photopolymerization, preferred light is polymerized, particularly UV photopolymerization.Here optionally also one or more initiators can be added.Be well known by persons skilled in the art for the suitable type of the suitable condition that is polymerized and initiator and amount thereof and be described in the literature.What be applicable to radical polymerization is such as the light trigger of commercially available acquisition or (Ciba AG).If use initiator, then its ratio is preferably 0.001 to 5 % by weight, is particularly preferably 0.001 to 1 % by weight.

Also be applicable to according to polymerizable compound of the present invention the polymerization not using initiator, which achieve considerable advantage, such as, the pollution of lower raw materials cost and the particularly less LC medium caused by initiator or its degraded product of possibility residual quantity.Therefore polymerization can also be carried out when not adding initiator.In a preferred embodiment, therefore LC medium does not comprise polymerization starter.

Polymerizable components A) or LC medium can also comprise one or more stablizers with prevent such as storage or the less desirable RM spontaneous polymerization of In transit.The suitable type of stablizer and amount are well known by persons skilled in the art and are described in the literature.Specially suitable be such as from the stablizer of the commercially available acquisition of series (Ciba AG), such as 1076.Based on RM or polymerizable components A) total amount, if use stablizer, its ratio is preferably 10-500, and 000ppm is particularly preferably 50-50,000ppm.

Polymerizable components A) or LC medium can also comprise one or more chiral dopants, such as, to induce distortion molecular structure.The chiral dopant of suitable type and amount is known to those skilled in the art and is described in document.Specially suitable chiral dopant R/S-811, R/S-1011, R/S-2011, R/S-3011, R/S-4011 or R/S-5011 (Merck KGaA) be such as purchased.If employing chiral dopant, then based on comprising component A) and B) both total LC medium, its ratio is preferably 0.001-15wt%, particularly preferably 0.1-5wt%.

In a further preferred embodiment, LC medium is not containing chipal compounds.

Preferably, according to LC medium of the present invention preferably substantially by one or more formula I polymerizable compound and as above LC body mixture hereinafter described form.But, LC medium or LC body mixture additionally can comprise one or more other components or additives, be preferably selected from such enumerating, include but not limited to comonomer, chiral dopant, polymerization starter, inhibitor, stablizer, tensio-active agent, wetting agent, lubricant, dispersion agent, hydrophobizing agent, tackiness agent, FLOW IMPROVERS, defoamer, air release agent, thinner, reactive diluent, auxiliary agent, tinting material, dyestuff, pigment and nano particle.

The LC medium being used for PSA indicating meter according to the present invention preferably comprises >0 to <5 % by weight, particularly preferably comprises >0 to <1 % by weight, very particularly preferably comprises the polymerizable compound, particularly formula I of 0.01 to 0.5 % by weight and the polymerizable compound of its minor.

Particularly preferably be comprise a kind of, two or three according to the LC medium of polymerizable compound of the present invention.

Further preferably, wherein polymerizable components (component A) only comprises the LC medium according to polymerizable compound of the present invention.

Further preferably, wherein B component) be there is nematic liquid crystal phase and preferably not there is the LC compound of chiral liquid crystal phase or the LC medium of LC mixture.

Further preferably according to achiral polymerisable compound of the present invention and wherein component A) and/or compound B) be only selected from the LC medium of non-chiral compound.

Further preferably wherein polymerizable components or component A) comprise one or more according to the present invention comprise a polymerizable groups (single reaction) polymerizable compound and one or more comprise two or more according to of the present invention, the preferably LC medium of the polymerizable compound of two polymerizable groups (two or multiple reactionness).

Further preferably, wherein polymerizable components or component A) only comprise the PSA indicating meter according to polymerizable compound of the present invention containing two polymerizable groups (double reactive) and LC medium.

In LC medium according to the present invention, polymerizable components or component A) ratio be preferably >0 to <5%, be particularly preferably >0 to <1%, be very particularly preferably 0.01 to 0.5%.

In LC medium according to the present invention, liquid crystal components or B component) ratio be preferably 95 to <100%, be particularly preferably 99 to <100%.

Can be separately polymerization according to polymerizable compound of the present invention, but also aggregate packet can contain two or more according to the mixture of polymerizable compound of the present invention, or comprising one or more according to the mixture of polymerizable compound of the present invention with one or more other polymerizable compounds (" comonomer "), other polymerizable compounds described are preferably mesomorphic or liquid crystal.When these polymerization of mixtures, multipolymer can be formed.The invention further relates to the polymerizable mixture mentioned in context.Polymerizable compound and comonomer are mesomorphic or non-mesogenic, and it is mesomorphic or liquid crystal preferably.

In preferred embodiments, LC medium contains one or more polymerizable compounds only with a polymerizable groups (single reaction) and one or more have the polymerizable compound of two or more polymerizable groups.

In another preferred embodiment, LC medium is only containing the polymerizable compound with two or more polymerizable groups.

In another preferred embodiment, LC medium is only containing the polymerizable compound just in time with three polymerizable groups.

In another preferred embodiment, LC medium, only containing the polymerizable compound being selected from formula I, very preferably just in time has the polymerizable compound of three polymerizable groups.

Suitable and mesogenic comonomers preferably and especially for PSA indicating meter is such as selected from following formula:

Wherein each group has following implication:

P ¹, P ²and P ³represent polymerizable thing group independently of one another separately, it has context is P ¹one of implication provided, is particularly preferably acrylate-based, methacrylate based, fluoro acrylic ester base, oxetanyl, vinyl, vinyloxy group or epoxy group(ing),

Sp ¹, Sp ²and Sp ³represent singly-bound or spacer groups independently of one another separately, it has in context is Sp ¹one of implication provided, and particularly preferably expression-(CH ₂) _p1-,-(CH ₂) _p1-O-,-(CH ₂) _p1-CO-O-,-(CH ₂) _p1-O-CO-or-(CH ₂) _p1-O-CO-O-, wherein p1 is the integer of 1 to 12, in addition, wherein group P ¹-Sp ¹-, P ¹-Sp ²-and P ³-Sp ³-in one or morely can represent R ^aa, its prerequisite is the group P existed ¹-Sp ¹-, P ²-Sp ²-and P ³-Sp ³-at least one and R ^aadifference,

R ^aarepresent H, F, Cl, CN or there is the straight or branched alkyl of 1 to 25 C atom, in addition, wherein one or more non-conterminous CH ₂group can independently of one another by C (R ⁰)=C (R ⁰⁰)-,-C ≡ C-,-N (R ⁰)-,-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-replace in the not direct interconnective mode of O and/or S atom, and in addition, wherein one or more H atom can by F, Cl, CN or P ¹-Sp ¹-replace, that be particularly preferably straight or branched, that there is 1 to 12 C atom preferred list or the alkyl in polyfluoro generation, alkoxyl group, thiazolinyl, alkynyl, alkyl-carbonyl, alkoxy carbonyl, alkyl carbonyl oxy or alkoxyl group carbonyl oxygen base (wherein thiazolinyl and alkynyl group there are at least two C atoms and the group of side chain has at least 3 C atoms).

R ⁰, R ⁰⁰it is separately independent of one another and identical or differently represent H or there is the alkyl of 1 to 12 C atom when occurring at every turn,

R ^yand R ^zrepresent H, F, CH independently of one another separately ₃or CF ₃,

X ¹, X ²and X ³represent-CO-O-,-O-CO-or singly-bound independently of one another separately,

Z ¹represent-O-,-CO-,-C (R ^yr ^z)-or-CF ₂cF ₂-,

Z ²and Z ³represent-CO-O-,-O-CO-,-CH independently of one another separately ₂o-,-OCH ₂-,-CF ₂o-,-OCF ₂-or-(CH ₂) _n-, wherein n is 2,3 or 4,

When L occurs at every turn identical differently represent F, Cl, CN or have 1 to 12 C atom straight or branched, optional list or the alkyl in polyfluoro generation, alkoxyl group, thiazolinyl, alkynyl, alkyl-carbonyl, alkoxy carbonyl, alkyl carbonyl oxy or alkoxyl group carbonyl oxygen base, be preferably F

L' and L " represent H, F or Cl independently of one another separately,

R represents 0,1,2,3 or 4,

S represents 0,1,2 or 3,

T represents 0,1 or 2,

X represents 0 or 1.

Particularly preferably be the compound of formula M1 to M28.

In the compound of formula M1 to M42, be preferably

Wherein L is identical or differently have one of implication that context provides when occurring at every turn, and is preferably F, Cl, CN, NO ₂, CH ₃, C ₂h ₅, C (CH ₃) ₃, CH (CH ₃) ₂, CH ₂cH (CH ₃) C ₂h ₅, OCH ₃, OC ₂h ₅, COCH ₃, COC ₂h ₅, COOCH ₃, COOC ₂h ₅, CF ₃, OCF ₃, OCHF ₂, OC ₂f ₅or P-Sp-, be very preferably F, Cl, CN, CH ₃, C ₂h ₅, OCH ₃, COCH ₃, OCF ₃or P-Sp-, be more preferably F, Cl, CH ₃, OCH ₃, COCH ₃or OCF ₃, be in particular F or CH ₃.

Except polymerizable compound described above, LC medium for LC indicating meter according to the present invention also comprises a kind of LC mixture (" body mixture "), this mixture comprises one or more, preferably two or more lower molecular weights (i.e. monomer or be not polymerized) compound.The latter is stable or non-reacted to polyreaction under the condition of being polymerized for polymerizable compound.In principle, any LC mixture being suitable for conventional VA and OCB indicating meter is all suitable as body mixture.Suitable LC mixture is well known by persons skilled in the art and is described in the literature, such as, for the mixture of OCB indicating meter in the mixture in the VA indicating meter in EP 1 378 557 A1 and EP 1 306 418 A1 and DE 102 24 046 A1.

Except the polymerizable compound of formula I, LC medium according to the present invention also comprises one or more mesomorphic comprising thiazolinyl (" olefin(e) compound ") or liquid crystalline cpds, and wherein this thiazolinyl is stable to polyreaction under the condition for the polymerizable compound of formula I or other being included in the polymerizable compound polymerization in LC medium.

Compared with the known reactive mesogen of prior art, the polymerizable compound of the formula I in this LC medium demonstrates the character of improvement, such as solvability, reactivity or produce the ability at pitch angle.

LC medium preferably comprises

-liquid crystal components B), hereinafter also referred to " LC body mixture ", it comprises one or more mesomorphic comprising thiazolinyl or liquid crystalline cpds.

LC body mixture preferred nematic LC mixture, and preferably not there is chirality LC phase.

Thiazolinyl in olefin(e) compound be preferably selected from particularly have 2 to 25 C atoms, the straight chain particularly preferably with 2 to 12 C atoms, side chain or cyclic alkenyl radical, in addition, wherein one or more non-conterminous CH ₂group can be replaced in the not direct interconnective mode of O and/or S atom by-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-, and in addition, wherein one or more H atom can be replaced by F and/or Cl.

Preferred thiazolinyl is straight-chain alkenyl and the cyclohexenyl with 2 to 7 C atoms, particularly vinyl (ethenyl (vinyl)), propenyl, butenyl, pentenyl, hexenyl, heptenyl, 1,4-tetrahydrobenzene-1-base and Isosorbide-5-Nitrae-tetrahydrobenzene-3-base.

In LC body mixture, the concentration comprising the compound (namely without any polymerizable compound) of thiazolinyl is preferably 5% to 100%, is very preferably 20% to 60%.

Particularly preferably be and comprise 1 to 5 kind, preferably comprise 1,2 or 3 kind of LC mixture with the compound of thiazolinyl.

The mesomorphic and the liquid crystalline cpd that comprise thiazolinyl are preferably selected from following formula:

Wherein each group is identical or differently have following implication independently of one another separately when occurring at every turn:

R ¹¹: the thiazolinyl with 2 to 9 C atoms, if or at least one representative ring hexenyl of ring X, Y and Z, then it also has R ^done of implication,

R ¹²: the alkyl with 1 to 12 C atom, in addition, wherein one or two non-conterminous CH ₂group can be replaced in the not direct interconnective mode of O atom by-O-,-CH=CH-,-CO-,-OCO-or-COO-,

Z ^x:-CH ₂cH ₂-,-CH=CH-,-CF ₂o-,-OCF ₂-,-CH ₂o-,-OCH ₂-,-CO-O-,-O-CO-,-C ₂f ₄-,-CF=CF-,-CH=CH-CH ₂o-or singly-bound, be preferably singly-bound,

L ^1-4: be H, F, Cl, OCF independently of one another separately ₃, CF ₃, CH ₃, CH ₂f or CHF ₂h, is preferably H, F or Cl,

X:1 or 2,

Z:0 or 1,

R ²²preferably there is the straight chained alkyl of 1 to 8 C atom or alkoxyl group or there is the straight-chain alkenyl of 2 to 7 C atoms.

LC medium does not preferably comprise the vinyloxy group (-O-CH=CH containing end ₂) compound, particularly do not comprise wherein R ¹¹or R ¹²represent or contain the vinyloxy group (-O-CH=CH of end ₂) formula A or the compound of B.

Preferably, L ¹and L ²represent F, or L ¹and L ²in one represent F and another represents Cl, and L ³and L ⁴represent F, or L ³and L ⁴in one represent F and another represent Cl.

The compound of formula AN is preferably selected from following minor:

Wherein alkyl represents the straight chained alkyl with 1-6 C atom, and alkenyl and alkenyl* represents the straight-chain alkenyl with 2-7 C atom separately independently of one another.Alkenyl and alkenyl* preferably represents CH ₂=CH-, CH ₂=CHCH ₂cH ₂-, CH ₃-CH=CH-, CH ₃-CH ₂-CH=CH-, CH ₃-(CH ₂) ₂-CH=CH-, CH ₃-(CH ₂) ₃-CH=CH-or CH ₃-CH=CH-(CH ₂) ₂-.

The compound of formula AY is preferably selected from following minor:

Formula AN compound is very particularly preferably selected from following minor:

Wherein m represent 1,2,3,4,5 or 6, i represent 0,1,2 or 3, and R ^b1represent H, CH ₃or C ₂h ₅.

Particularly preferably be following compound:

The most preferably compound of formula AN1a1.

The compound of formula AY is very particularly preferably selected from following minor:

Wherein m and n represent independently of one another separately 1,2,3,4,5 or 6, i represent 0,1,2 or 3, R ^b1represent H, CH ₃or C ₂h ₅, and alkenyl represents CH ₂=CH-, CH ₂=CHCH ₂cH ₂-, CH ₃-CH=CH-, CH ₃-CH ₂-CH=CH-, CH ₃-(CH ₂) ₂-CH=CH-, CH ₃-(CH ₂) ₃-CH=CH-or CH ₃-CH=CH-(CH ₂) ₂-.

In first preferred embodiment, LC medium comprises the LC body mixture based on the compound with negative dielectric anisotropy.This LC medium is particularly suitable for PSA-VA indicating meter.The particularly preferred embodiment of this LC medium and corresponding LC body mixture is following a)-y) those in part:

A) the LC medium of the compound of one or more formula CY and/or PY is comprised:

Wherein:

A represents 1 or 2,

B represents 0 or 1,

represent

R ¹and R ²represent the alkyl with 1 to 12 C atom separately independently of one another, in addition, wherein one or two non-conterminous CH ₂group can be replaced in the not direct interconnective mode of O atom by-O-,-CH=CH-,-CO-,-OCO-or-COO-, preferably has alkyl or the alkoxyl group of 1 to 6 C atom,

Z ^xand Z ^yrespective expression-CH independently of one another ₂cH ₂-,-CH=CH-,-CF ₂o-,-OCF ₂-,-CH ₂o-,-OCH ₂-,-CO-O-,-O-CO-,-C ₂f ₄-,-CF=CF-,-CH=CH-CH ₂o-or singly-bound, be preferably singly-bound,

L ^1-4represent F, Cl, OCF independently of one another separately ₃, CF ₃, CH ₃, CH ₂f, CHF ₂,

Preferably, L ¹and L ²represent F, or L ¹and L ²in one represent F and another represents Cl, and L ³and L ⁴all represent F, or L ³and L ⁴in one represent F and another represent Cl.

The compound of formula CY is preferably selected from following minor:

Wherein a represents that 1 or 2, alkyl and alkyl* represent the straight chained alkyl with 1-6 C atom separately independently of one another, and alkenyl represents the straight-chain alkenyl with 2-6 C atom, and (O) represents Sauerstoffatom or singly-bound.Alkenyl preferably represents CH ₂=CH-, CH ₂=CHCH ₂cH ₂-, CH ₃-CH=CH-, CH ₃-CH ₂-CH=CH-, CH ₃-(CH ₂) ₂-CH=CH-, CH ₃-(CH ₂) ₃-CH=CH-or CH ₃-CH=CH-(CH ₂) ₂-.

The compound of formula PY is preferably selected from following minor:

Wherein alkyl and alkyl* represents the straight chained alkyl with 1-6 C atom separately independently of one another, and alkenyl represents the straight-chain alkenyl with 2-6 C atom, and (O) represents Sauerstoffatom or singly-bound.Alkenyl preferably represents CH ₂=CH-, CH ₂=CHCH ₂cH ₂-, CH ₃-CH=CH-, CH ₃-CH ₂-CH=CH-, CH ₃-(CH ₂) ₂-CH=CH-, CH ₃-(CH ₂) ₃-CH=CH-or CH ₃-CH=CH-(CH ₂) ₂-.

B) the LC medium of one or more following formula: compounds is additionally comprised:

Wherein each group has following implication:

represent

R ³and R ⁴represent the alkyl with 1 to 12 C atom separately independently of one another, in addition, wherein one or two non-conterminous CH ₂group can be replaced in the not direct interconnective mode of O atom by-O-,-CH=CH-,-CO-,-O-CO-or-CO-O-,

Z ^yexpression-CH ₂cH ₂-,-CH=CH-,-CF ₂o-,-OCF ₂-,-CH ₂o-,-OCH ₂-,-CO-O-,-O-CO-,-C ₂f ₄-,-CF=CF-,-CH=CH-CH ₂o-or singly-bound, be preferably singly-bound.

The compound of formula ZK is preferably selected from following minor:

Wherein alkyl and alkyl* represents the straight chained alkyl with 1-6 C atom separately independently of one another, and alkenyl represents the straight-chain alkenyl with 2-6 C atom.Alkenyl preferably represents CH ₂=CH-, CH ₂=CHCH ₂cH ₂-, CH ₃-CH=CH-, CH ₃-CH ₂-CH=CH-, CH ₃-(CH ₂) ₂-CH=CH-, CH ₃-(CH ₂) ₃-CH=CH-or CH ₃-CH=CH-(CH ₂) ₂-.

C) the LC medium of one or more following formula: compounds is additionally comprised:

Wherein each group is identical or differently have following implication when occurring at every turn:

R ⁵and R ⁶separately there is above R independently of one another ¹one of implication represented,

represent

represent and

E represents 1 or 2.

The compound of formula DK is preferably selected from following minor:

Wherein alkyl and alkyl* represents the straight chained alkyl with 1-6 C atom separately independently of one another, and alkenyl and alkenyl* represents the straight-chain alkenyl with 2-6 C atom separately independently of one another.Alkenyl and alkenyl* preferably represents CH ₂=CH-, CH ₂=CHCH ₂cH ₂-, CH ₃-CH=CH-, CH ₃-CH ₂-CH=CH-, CH ₃-(CH ₂) ₂-CH=CH-, CH ₃-(CH ₂) ₃-CH=CH-or CH ₃-CH=CH-(CH ₂) ₂-.

D) the LC medium of one or more following formula: compounds is additionally comprised:

Wherein each group has following implication:

represent

F represents 0 or 1,

R ¹and R ²represent the alkyl with 1 to 12 C atom separately independently of one another, in addition, wherein one or two non-conterminous CH ₂group can be replaced in the not direct interconnective mode of O atom by-O-,-CH=CH-,-CO-,-OCO-or-COO-,

L ¹and L ²represent F, Cl, OCF independently of one another separately ₃, CF ₃, CH ₃, CH ₂f, CHF ₂,

Preferably, group L ¹and L ²all represent F, or L ¹and L ²in one represent F and another represent Cl.

The compound of formula LY is preferably selected from following minor:

Wherein R ¹have above shown implication, alkyl represents the straight chained alkyl with 1-6 C atom, and (O) represents Sauerstoffatom or singly-bound, and v represents the integer of 1 to 6.R ¹preferred expression has the straight chained alkyl of 1 to 6 C atom or has the straight-chain alkenyl, particularly CH of 2 to 6 C atoms ₃, C ₂h ₅, n-C ₃h ₇, n-C ₄h ₉, n-C ₅h ₁₁, CH ₂=CH-, CH ₂=CHCH ₂cH ₂-, CH ₃-CH=CH-, CH ₃-CH ₂-CH=CH-, CH ₃-(CH ₂) ₂-CH=CH-, CH ₃-(CH ₂) ₃-CH=CH-or CH ₃-CH=CH-(CH ₂) ₂-.

E) the LC medium that one or more are selected from the compound of following formula is additionally comprised:

Wherein alkyl represents C _1-6-alkyl, L ^xrepresent H or F, and X represents F, Cl, OCF ₃, OCHF ₂or OCH=CF ₂.Particularly preferably be the compound that wherein X represents the formula G1 of F.

F) the LC medium that one or more are selected from the compound of following formula is additionally comprised:

Wherein R ⁵there is above R ¹one of implication represented, alkyl represents C _1-6-alkyl, d represents 0 or 1, and z and m represents the integer of 1 to 6 separately independently of one another.R in these compounds ⁵be particularly preferably C _1-6-alkyl or-alkoxyl group or C _2-6-thiazolinyl, d is preferably 1.Preferably the compound of one or more above-mentioned formulas is comprised with the amount of >=5 % by weight according to LC medium of the present invention.

G) the LC medium that one or more are selected from the biphenyl compounds of following formula is additionally comprised:

The ratio of the biphenyl compounds in LC mixture Chinese style B1 to B3 is preferably at least 3 % by weight, be in particular >=5 % by weight.

The compound of formula B2 is particularly preferred.

The compound of formula B1 to B3 is preferably selected from following minor:

Wherein alkyl* represents the alkyl with 1-6 C atom.The compound of one or more formula B1a and/or B2c is particularly preferably comprised according to medium of the present invention.

H) the LC medium of the terphenyl compound of one or more following formulas is additionally comprised:

Wherein R ⁵and R ⁶separately there is above R independently of one another ¹one of shown implication, and

Represent independently of one another separately

Wherein L ⁵represent F or Cl, be preferably F, and L ⁶represent F, Cl, OCF ₃, CF ₃, CH ₃, CH ₂f or CHF ₂, be preferably F.

The compound of formula T is preferably selected from following minor:

Wherein R represents the straight chained alkyl or alkoxyl group with 1-7 C atom, and R* represents the straight-chain alkenyl with 2-7 C atom, and (O) represents Sauerstoffatom or singly-bound, and m represents the integer of 1 to 6.R* preferably represents CH ₂=CH-, CH ₂=CHCH ₂cH ₂-, CH ₃-CH=CH-, CH ₃-CH ₂-CH=CH-, CH ₃-(CH ₂) ₂-CH=CH-, CH ₃-(CH ₂) ₃-CH=CH-or CH ₃-CH=CH-(CH ₂) ₂-.

R preferably represents methyl, ethyl, propyl group, butyl, amyl group, hexyl, methoxyl group, oxyethyl group, propoxy-, butoxy or phenoxy group.

According to LC medium of the present invention preferably with 0.5-30 % by weight, especially with the terphenyl compounds of the contained T of the amount of 1-20 % by weight and preferred minor thereof.

Particularly preferably be the compound of formula T1, T2, T3 and T21.In these compounds, R preferably represents alkyl, also represents alkoxyl group, and each has 1-5 C atom.

If Δ n value >=0.1 of mixture, then preferably in mixture according to the present invention, use terphenyl compounds.Preferred mixture comprises the terphenyl compounds of one or more formula T of 2-20 % by weight, is preferably selected from compound T1 to T22.

I) the LC medium that one or more are selected from following formula: compound is additionally comprised:

Wherein R ¹and R ²there is above shown implication and preferably represent independently of one another separately and there is the straight chained alkyl of 1 to 6 C atom or there is the straight-chain alkenyl of 2 to 6 C atoms.

Preferred medium comprises the compound that one or more are selected from formula O1, O3 and O4.

K) the LC medium of one or more following formula: compounds is additionally comprised:

Wherein

represent

R ⁹represent H, CH ₃, C ₂h ₅or n-C ₃h ₇, (F) represents optional fluoro substituents, and q represents 1,2 or 3, and R ⁷there is R ¹one of shown implication, preferably its amount is >3 % by weight, be in particular>=5 % by weight, and be very particularly preferably 5-30 % by weight.

The compound of particularly preferred formula FI is selected from following minor:

Wherein R ⁷preferred expression straight chained alkyl, and R ⁹represent CH ₃, C ₂h ₅or n-C ₃h ₇.Particularly preferably be the compound of formula FI1, FI2 and FI3.

L) the LC medium that one or more are selected from the compound of following formula is additionally comprised:

Wherein R ⁸there is R ¹shown implication, and alkyl represents the straight chained alkyl with 1-6 C atom.

M) additionally comprise the LC medium that one or more comprise the compound of tetralyl or naphthyl unit, such as, be selected from the compound of following formula:

Wherein R ¹⁰and R ¹¹independently of one another there is R separately ¹one of shown implication, preferably represents straight chained alkyl or the alkoxyl group with 1 to 6 C atom, or has the straight-chain alkenyl of 2 to 6 C atoms, and Z ¹and Z ²respective expression-C independently of one another ₂h ₄-,-CH=CH-,-(CH ₂) ₄-,-(CH ₂) ₃o-,-O (CH ₂) ₃-,-CH=CH-CH ₂cH ₂-,-CH ₂cH ₂cH=CH-,-CH ₂o-,-OCH ₂-,-CO-O-,-O-CO-,-C ₂f ₄-,-CF=CF-,-CF=CH-,-CH=CF-,-CH ₂-or singly-bound.

N) difluorodiphenyl of one or more following formulas is additionally comprised and the LC medium of chroman and/or chroman:

Wherein

R ¹¹and R ¹²there is above shown implication separately independently of one another,

Ring M is anti-form-1,4-cyclohexylene or Isosorbide-5-Nitrae-phenylene,

Z ^m-C ₂h ₄-,-CH ₂o-,-OCH ₂-,-CO-O-or-O-CO-,

C is 0 or 1,

Preferably its amount is 3 to 20 % by weight, is in particular the amount of 3 to 15 % by weight.

The compound of particularly preferred formula BC, CR and RC is selected from following minor:

Wherein alkyl and alkyl* represents the straight chained alkyl with 1-6 C atom separately independently of one another, (O) Sauerstoffatom or singly-bound is represented, c is 1 or 2, and alkenyl and alkenyl* represents the straight-chain alkenyl with 2-6 C atom separately independently of one another.Alkenyl and alkenyl* preferably represents CH ₂=CH-, CH ₂=CHCH ₂cH ₂-, CH ₃-CH=CH-, CH ₃-CH ₂-CH=CH-, CH ₃-(CH ₂) ₂-CH=CH-, CH ₃-(CH ₂) ₃-CH=CH-or CH ₃-CH=CH-(CH ₂) ₂-.

Very particularly preferably be the mixture of the compound comprising a kind of, two or three formula BC-2.

O) the fluoro phenanthrene of one or more following formulas and/or the LC medium of diphenylene-oxide is additionally comprised:

Wherein R ¹¹and R ¹²have independently of one another separately above shown in implication, b represent 0 or 1, L represent F, and r represents 1,2 or 3.

The particularly preferred compound of formula PH and BF is selected from following minor:

Wherein R and R' represents straight chained alkyl or the alkoxyl group with 1-7 C atom separately independently of one another.

P) the LC medium of the monocyclic compound of one or more following formulas is additionally comprised:

Wherein:

L ¹and L ²represent F, Cl, OCF independently of one another separately ₃, CF ₃, CH ₃, CH ₂f, CHF ₂.

Preferably, L ¹and L ²all represent F or L ¹and L ²in one represent F and another represent Cl.

The compound of formula Y is preferably selected from following minor:

Wherein Alkyl and Alkyl* represents the straight chained alkyl with 1-6 C atom separately independently of one another, Alkoxy represents the unbranched alkoxy with 1-6 C atom, Alkenyl and Alkenyl* represents the straight-chain alkenyl with 2-6 C atom separately independently of one another, and O represents Sauerstoffatom or singly-bound.Alkenyl and Alkenyl* preferably represents CH ₂=CH-, CH ₂=CHCH ₂cH ₂-, CH ₃-CH=CH-, CH ₃-CH ₂-CH=CH-, CH ₃-(CH ₂) ₂-CH=CH-, CH ₃-(CH ₂) ₃-CH=CH-or CH ₃-CH=CH-(CH ₂) ₂-.

The compound of particularly preferred formula Y is selected from following minor:

Wherein Alkoxy preferably represents the unbranched alkoxy with 3,4 or 5 C atoms.

Q) except according to except of the present invention, particularly formula I and minor thereof polymerizable compound and comonomer, the vinyloxy group (-O-CH=CH containing end is not comprised ₂) the LC medium of compound.

R) 1 to 5 kind is comprised, preferably 1,2 or 3 kind of polymerizable compound, be preferably selected from LC medium according to of the present invention, particularly formula I and minor thereof polymerizable compound.

S) wherein the ratio of the polymerizable compound of polymerizable compound, particularly formula I and minor thereof is 0.05 to 5% in whole mixture, preferably the LC medium of 0.1 to 1%.

T) comprise 1 to 8, the LC medium of the preferred compound of 1 to 5 kind of formula CY1, CY2, PY1 and/or PY2.The ratio of these compounds is preferably 5 to 60% in whole mixture, is particularly preferably 10 to 35%.The content of these independent compounds is preferably all 2 to 20% in each case.

U) comprise 1 to 8, the LC medium of the preferred compound of 1 to 5 kind of formula CY9, CY10, PY9 and/or PY10.The ratio of these compounds is preferably 5 to 60% in whole mixture, is particularly preferably 10 to 35%.The content of these independent compounds is preferably all 2 to 20% in each case.

V) comprise 1 to 10, the LC medium of the preferably compound, particularly formula ZK1 of 1 to 8 kind of formula ZK, the compound of ZK2 and/or ZK6.The ratio of these compounds is preferably 3 to 25% in whole mixture, is particularly preferably 5 to 45%.The content of these independent compounds is preferably all 2 to 20% in each case.

W) LC medium, the ratio of the compound of its Chinese style CY, PY and ZK is greater than 70%, is preferably greater than 80% in whole mixture.

X) wherein LC body mixture comprises one or more LC media containing the compound of thiazolinyl, and the described compound containing thiazolinyl is preferably selected from formula CY, PY and LY, wherein R ¹and R ²in one or two represent that there is the straight-chain alkenyl of 2-6 C atom; Formula ZK and DK, wherein R ³and R ⁴in one or two all represent the straight-chain alkenyl with 2-6 C atom, and formula B2 and B3; Very preferably be selected from formula CY15, CY16, CY34, CY32, PY15, PY16, ZK3, ZK4, DK3, DK6, B2 and B3, be most preferably selected from formula ZK3, ZK4, B2 and B3.The concentration of these compounds in LC body mixture is preferably 2 to 70%, is very preferably 3 to 55%.

Y) comprise one or more, preferably 1 to 5 kind is selected from the compound of formula PY1-PY8, is very preferably the LC medium of the compound of formula PY2.The ratio of these compounds is preferably 1 to 30% in whole mixture, is particularly preferably 2 to 20%.The content of these independent compounds is preferably all 1 to 20% in each case.

Z) one or more are comprised, preferably 1,2 or the LC medium of compound of 3 kind of formula T2.The content of these compounds is preferably 1 to 20% in whole mixture.

In second preferred embodiment, LC medium comprises the LC body mixture based on the compound with positive dielectric anisotropy.This LC medium is particularly suitable for PSA-OCB-, PSA-TN-, PSA-positivity-VA-, PSA-IPS-or PSA-FFS indicating meter.

Particularly preferably be LC medium and the LC body mixture of this second preferred version, it comprises the compound that one or more are selected from the compound of formula AA and BB,

And except the compound of formula AA and/or BB, it also optionally comprises the compound of one or more formula CC,

Wherein each group has following implication:

separately independent of one another and identical or differently represent when occurring at every turn

R ²¹, R ³¹, R ⁴¹, R ⁴²be separately that there is the alkyl of 1 to 9 C atom, alkoxyl group, oxa alkyl or fluoro-alkyl independently of one another, or there is the thiazolinyl of 2 to 9 C atoms,

X ⁰f, Cl, the haloalkyl with 1 to 6 C atom or alkoxyl group, or there is haloalkenyl group or the thiazolinyl oxygen base of 2 to 6 C atoms,

Z ³¹-CH ₂cH ₂-,-CF ₂cF ₂-,-COO-, trans-CH=CH-, trans-CF=CF-,-CH ₂o-or singly-bound, be preferably-CH ₂cH ₂-,-COO-, trans-CH=CH-or singly-bound, be particularly preferably-COO-, trans-CH=CH-or singly-bound,

Z ⁴¹, Z ⁴²-CH ₂cH ₂-,-COO-, trans-CH=CH-, trans-CF=CF-,-CH ₂o-,-CF ₂o-,-C ≡ C-or singly-bound, be preferably singly-bound,

L ²¹, L ²², L ³¹, L ³²h or F,

G is 1,2 or 3,

H is 0,1,2 or 3.

X ⁰be preferably F, Cl, CF ₃, CHF ₂, OCF ₃, OCHF ₂, OCFHCF ₃, OCFHCHF ₂, OCFHCHF ₂, OCF ₂cH ₃, OCF ₂cHF ₂, OCF ₂cHF ₂, OCF ₂cF ₂cHF ₂, OCF ₂cF ₂cHF ₂, OCFHCF ₂cF ₃, OCFHCF ₂cHF ₂, OCF ₂cF ₂cF ₃, OCF ₂cF ₂cClF ₂, OCClFCF ₂cF ₃or CH=CF ₂, very preferably F or OCF ₃.

The compound of formula AA is preferably selected from following formula:

Wherein A ²¹, R ²¹, X ⁰, L ²¹and L ²²there is the implication provided in formula AA, L ²³and L ²⁴be H or F, X independently of one another separately ⁰be preferably F.Particularly preferably be the compound of formula AA1 and AA2.

The compound of particularly preferred formula AA1 is selected from following minor:

Wherein R ⁰there is the R provided in formula AA1 ²¹one of implication, X ⁰, L ²¹and L ²²there is the implication provided in formula AA1, L ²³, L ²⁴, L ²⁵and L ²⁶be H or F independently of one another separately, and X ⁰be preferably F.

The compound of formula AA1 is very particularly preferably selected from following minor:

Wherein R ⁰there is the R provided in formula AA1 ²¹implication.

The compound of formula AA2 is very particularly preferably selected from following minor:

Wherein R ⁰there is the R provided in formula AA1 ²¹implication, X ⁰, L ²¹and L ²²there is the implication provided in formula AA, L ²³, L ²⁴, L ²⁵and L ²⁶be H or F independently of one another separately, and X ⁰be preferably F.

Wherein R ⁰there is the R provided in formula AA1 ²¹implication.

The compound of particularly preferred formula AA3 is selected from following minor:

Wherein, R ⁰there is the R provided in formula AA1 ²¹implication, X ⁰, L ²¹and L ²²there is the implication provided in formula AA3, and X ⁰be preferably F.

The compound of particularly preferred formula AA4 is selected from following minor:

Wherein R ⁰there is the R provided in formula AA1 ²¹implication.

The compound of formula BB is preferably selected from following formula:

Wherein A ³¹, A ³², R ³¹, X ⁰, L ³¹and L ³²there is the implication provided in formula BB, and X ⁰be preferably F.Particularly preferably be the compound of formula BB1 and BB2.

The compound of particularly preferred formula BB1 is selected from following minor:

Wherein R ³there is the R provided in formula BB1 ³¹implication, X ⁰, L ³¹and L ³²there is the implication provided in formula BB1, and X ⁰be preferably F.

The compound of formula BB1a is very particularly preferably selected from following minor:

Wherein R ³there is the R provided in formula BB1 ³¹implication.

The compound of formula BB1b is very particularly preferably selected from following minor:

Wherein R ³there is the R provided in formula BB1 ³¹implication.

The compound of particularly preferred formula BB2 is selected from following minor:

Wherein R ⁰there is the R provided in formula BB2 ²¹one of implication, X ⁰, L ³¹and L ³²there is the implication provided in formula BB2, L ³³, L ³⁴, L ³⁵and L ³⁶be H or F, X independently of one another separately ⁰be preferably F.

The compound of formula BB2 is very particularly preferably selected from following minor:

Wherein R ³there is the R provided in formula BB2 ³¹implication.

The compound of formula BB2b is very particularly preferably selected from following minor:

Wherein R ³there is the R provided in formula BB2 ³¹implication.

The compound of formula BB2c is very particularly preferably selected from following minor:

Wherein R ³there is the R provided in formula BB2 ³¹implication.

Formula BB2d very particularly preferably and the compound of BB2e are selected from following minor:

Wherein R ³there is the R provided in formula BB2 ³¹implication.

The compound of formula BB2f is very particularly preferably selected from following minor:

Wherein R ³there is the R provided in formula BB2 ³¹implication.

The compound of formula BB2g is very particularly preferably selected from following minor:

Wherein R ³there is the R provided in formula BB2 ³¹implication.

The compound of formula BB2h is very particularly preferably selected from following minor:

Wherein R ³there is the R provided in formula BB2 ³¹implication.

The compound of formula BB2i is very particularly preferably selected from following minor:

Wherein R ³there is the R provided in formula BB2 ³¹implication.

The compound of formula BB2k is very particularly preferably selected from following minor:

Wherein R ³there is the R provided in formula BB2 ³¹implication.

Alternatively or except the compound of formula BB1 and/or BB2, LC medium can also comprise the compound of one or more formula BB3 as defined above.

The compound of particularly preferred formula BB3 is selected from following minor:

Wherein R ³there is the R provided in formula BB3 ³¹implication.

Preferably, according to the LC medium of the present invention's second preferred embodiment except the compound of formula AA and/or BB, also comprise one or more electroneutral compounds that is situated between, this compound has the dielectric anisotropy in-1.5 to+3 scopes, and it is preferably selected from the compound of formula CC as defined above.

The compound of particularly preferred formula CC is selected from following minor:

Wherein R ^41aand R ⁴²there is the implication provided in formula CC, and preferably represent alkyl, alkoxyl group, fluoro-alkyl or the fluoroalkyl with 1 to 7 C atom separately independently of one another, or there is the thiazolinyl of 2 to 7 C atoms, thiazolinyl oxygen base, alkoxyalkyl or fluoro thiazolinyl, and L ⁴h or F.

Preferably, according to the LC medium of the present invention's second preferred embodiment except or substituted CC dielectric neutral compound except, also comprise one or more dielectric neutral compounds, this compound has the dielectric anisotropy in-1.5 to+3 scopes, and it is selected from the compound of formula DD.

Wherein A ⁴¹, A ⁴², Z ⁴¹, Z ⁴², R ⁴¹, R ⁴²with h, there is the implication provided in formula CC.

The compound of particularly preferred formula DD is selected from following minor:

Wherein R ⁴¹and R ⁴²there is the implication provided in formula DD, and R ⁴¹preferred expression alkyl, and in formula DD1, R ⁴²preferred expression thiazolinyl, particularly preferably expression-(CH ₂) ₂-CH=CH-CH ₃, and in formula DD2 R ⁴²preferred expression alkyl ,-(CH ₂) ₂-CH=CH ₂or-(CH ₂) ₂-CH=CH-CH ₃.

The compound of formula AA and BB preferably in whole mixture with 2% to 60%, more preferably with 3% to 35%, and to be particularly preferably used for according in LC medium of the present invention with the concentration of 4% to 30%.

The compound of formula CC and DD preferably in whole mixture with 2% to 70%, more preferably with 5% to 65%, even more preferably with 10% to 60% and very particularly preferably with 10%, be preferably used for according in LC medium of the present invention with the concentration of 15% to 55%.

The compound of above-mentioned preferred embodiment and the combination of the above-mentioned compound be polymerized, low threshold voltage, low rotary viscosity and extraordinary low-temperature stability is achieved according to LC medium of the present invention, there are constant high clearing point and high HR value simultaneously, and allow set up pre-tilt angle low especially rapidly in PSA-indicating meter.Especially, this LC medium demonstrates the time of response significantly shortened in PSA-indicating meter relative to the medium of prior art, particularly also has the gray-tone response time.

Liquid crystal compound preferably has the nematic phase range of at least 80K, particularly preferably at least 100K, and at 20 DEG C not higher than 250mPas, preferably not higher than 200mPas, very preferably not higher than the rotary viscosity of 150mPas.

In VA types of display according to the present invention, at the layer Middle molecule of LC medium in the power-off state perpendicular to electrode surface (vertical plane ground) orientation or the vertical plane orientation with inclination.When applying voltage to electrode, there is molecule longitudinal axis in the orientation again of the LC molecule of electrode surface.

In particular in the indicating meter of PSA-VA type according to the first preferred embodiment, based on the LC medium of the present invention of the compound with negative dielectric anisotropic, there is negative dielectric anisotropy Δ ε, to be preferably under 20 DEG C and 1kHz from-0.5 to-10, particularly from-2.5 to-7.5.

For PSA-VA types of display according to degree of birefringence Δ n in LC medium of the present invention preferably lower than 0.16, particularly preferably from 0.06 to 0.14, very particularly preferably from 0.07 to 0.12.

In OCB-types of display according to the present invention, at the layer Middle molecule of LC medium, there is " bending " orientation.When applying voltage, there is molecule axis oriented normal in the orientation again of the LC molecule of electrode surface.

For the LC medium according to invention in the indicating meter of PSA-OCB type, preferably according to the second preferred specific embodiments based on those of compound with positive dielectric anisotropy, and preferably there is the positive dielectric anisotropy Δ ε of under 20 DEG C with 1kHz from+4 to+17.

According to of the present invention for the LC medium of PSA-OCB escope in degree of birefringence Δ n preferably between 0.14 and 0.22, particularly preferably between 0.16 and 0.22.

Based on according to the second preferred embodiment there is the compound of positive dielectric anisotropy preferably to have under 20 DEG C and 1kHz from+2 to+30, the particularly preferably positive dielectric anisotropy Δ ε of from+3 to+20 for the LC medium of the present invention in the indicating meter of PSA-TN-, PSA-positivity-VA-, PSA-IPS-or PSA-FFS-type.

Being preferably from 0.07 to 0.15, particularly preferably from 0.08 to 0.13 according to degree of birefringence Δ n in LC medium of the present invention in the indicating meter for PSA-TN-, PSA-positivity-VA-, PSA-IPS-or PSA-FFS-type.

LC medium according to the present invention can also comprise other additives that those skilled in the art are known and describe in the literature, such as polymerization starter, inhibitor, stablizer, surfactant or chiral dopant.These can be polymerisable or not polymerisable.Correspondingly, polymerisable additive is sorted out into polymerizable components or component A).Correspondingly, not polymerisable additive is sorted out into not polymerizable components or B component).

In preferred embodiments, LC medium contains one or more chiral dopants, preferably with the concentration of 0.01-1%, very preferably 0.05-0.5%.Chiral dopant is preferably selected from the compound of following table B, very preferably R-or S-1011, R-or S-2011, R-or S-3011, R-or S-4011 and R-or S-5011.

In another preferred embodiment, LC medium contains the racemoid of one or more chiral dopants, and it is preferably selected from the chiral dopant mentioned in the preceding paragraphs.

In addition the pleochroism dyestuff of such as 0 to 15 % by weight can be added LC medium, and also have nano particle, conducting salt, the complex salts of preferred 4-hexyloxybenzoate ethyl dimethyl dodecyl base ammonium, tetraphenylboronic acid TBuA or crown ether is (such as with reference to Haller etc., Mol.Cryst.Liq.Cryst.24,249-258 (1973)) improve electroconductibility, or for changing the material of dielectric anisotropy, viscosity and/or nematic phase orientation.This kind of substance description is in such as DE-A-2209127,2240864,2321632,2338281,2450088,2637430 and 2853728.

Preferred embodiment a)-z according to LC medium of the present invention) each component or known, or those skilled in the art easily can derive their preparation method from prior art, because they are based on the standard method described in document.Corresponding formula CY compound is described in such as EP-A-0364538.Corresponding formula ZK compound is described in such as DE-A-2636684 and DE-A-3321373.

LC medium that can be used according to the invention is prepared in a per se conventional manner, such as, pass through one or more above-claimed cpds and one or more polymerizable compounds as defined above, and optionally mix with other LC compound and/or additive.Usually, by desired amt, with lesser amt use components dissolved in the component being formed main component, advantageously carry out at elevated temperatures.Also can blending ingredients in organic solvent, such as, solution in acetone, chloroform or methyl alcohol, and after mixing thoroughly such as by distillation again except desolventizing.The invention still further relates to the method for preparation according to LC medium of the present invention.

To those skilled in the art without it should be noted that, wherein such as H, N, O, Cl, F also can be comprised by compound that corresponding isotropic substance is replaced according to LC medium of the present invention.

Correspond to the geometry conventional for PSA-indicating meter according to the structure of LC indicating meter of the present invention, as when starting described in the prior art quoted.Preferably without protruding geometrical shape, particularly wherein other electrode on colour filter side is not structured and electrode only on TFT side has those of otch.Suitable especially and electrode structure that is preferred PSA-VA indicating meter is described in such as US 2006/0066793A1.

Following embodiment has set forth the present invention, but is not limited.But they show the preferred mixture design of the compound that has and preferably use and its concentration and its combination with one another separately to those skilled in the art.In addition, these embodiments have been set forth and can have been obtained which kind of performance and combining properties.

Use following abbreviation:

(n, m, z: they are 1,2,3,4,5 or 6 independently of one another in each case)

table A

In a preferred embodiment of the present invention, LC medium according to the present invention comprises the compound that one or more are selected from the compound of Table A.

table B

Table B shows the possible chiral dopant that can add to according in LC medium of the present invention.

R/S-1011

The doping agent that LC medium preferably comprises 0 to 10 % by weight, comprise 0.01 to 5 % by weight especially, particularly preferably comprise 0.1 to 3 % by weight.LC medium preferably comprises the doping agent that one or more are selected from the compound of table B.

table C

Table C shows the possible stablizer that can add to according in LC medium of the present invention.

(at this, n represents the integer of 1 to 12, is preferably 1,2,3,4,5,6,7 or 8, does not show the methyl of end).

The stablizer that LC medium preferably comprises 0 to 10 % by weight, comprises 1ppm to 5 % by weight especially, particularly preferably comprises 1ppm to 1 % by weight.LC medium preferably comprises the stablizer that one or more are selected from the group be made up of the compound from table C.

table D

Table D shows the exemplary compound that may be used for according to LC medium of the present invention, and it is preferably as reactive mesogen compound.

In the present invention's preferred embodiment, mesogenic media comprises the compound that one or more are selected from the compound of table D.

In addition, following abbreviation and symbol is also used:

V ₀threshold voltage, capacitive character [V], at 20 DEG C,

N _eextraordinary refractive index under 20 DEG C and 589nm,

N _othe ordinary index of refraction under 20 DEG C and 589nm,

Optical anisotropy under Δ n 20 DEG C and 589nm,

ε _⊥perpendicular to the dielectric susceptibility of director under 20 DEG C and 1kHz,

ε _||the dielectric susceptibility of director is parallel under 20 DEG C and 1kHz,

Dielectric anisotropy under Δ ε 20 DEG C and 1kHz,

Cl.p., clearing point [DEG C],

T(N,I)

γ ₁rotary viscosity [mPas] at 20 DEG C,

K ₁elastic constant, " the tiltedly opening up " distortion [pN] at 20 DEG C,

K ₂elastic constant, " distortion " distortion [pN] at 20 DEG C,

K ₃elastic constant, " bending " distortion [pN] at 20 DEG C.

Unless otherwise expressly stated, all concentration in the application provide with weight percent, and to comprise all solids or liquid crystal components accordingly and there is no the whole mixture of solvent.

Unless expressly stated otherwise, the value of all temperature indicated in this application, as fusing point T (C, N), from smectic (S) mutually to the transformation T (S to row (N) phase, N) and clearing point T (N, I), all represent with centigradetemperature (DEG C).M.p. fusing point is represented, cl.p.=clearing point.In addition, C=crystal form, N=nematic phase, S=smectic phase and I=isotropic phase.Data representation transition temperature between these symbols.

All physicalies are according to " Merck Liquid Crystals; Physical Propertiesof Liquid Crystals ", Status in November, 1997, that Merck KGaA (Germany) measures and Applicable temperature 20 DEG C, and Δ n determines at 1 khz, unless explicitly pointed out in addition under often kind of situation with Δ ε under 589nm.

For the present invention, term " threshold voltage " refers to capacitive character threshold value (V ₀), also referred to as Freedericks-threshold value, unless otherwise expressly stated.In embodiment, as commonly, also can provide the optical threshold (V for 10% relative contrast ₁₀).

Except as otherwise noted, in as above PSA indicating meter hereinafter described, the process of polymerizing polymerizable compound is carried out under liquid crystal media demonstrates mesomorphic phase, preferred nematic temperature, most preferably at room temperature carries out.

Except as otherwise noted, prepare testing cassete and measure their electrooptics character and the method for other character and undertaken by method described below or the method that is similar to it.

Indicating meter for measuring capacitive character threshold voltage is made up of two that are spaced apart 25 μm parallel plane glass outside plates, described outside plate each there is electrode layer on inner side and be positioned at top, without the polyimide alignment layer of friction, it causes the edge orientation of the vertical plane of liquid crystal molecule.

Indicating meter or testing cassete for measuring pitch angle are made up of two that are spaced apart 4 μm parallel plane glass outside plates, the each of described outside plate has electrode layer and is positioned at the polyimide alignment layer at top on inner side, wherein said two polyimide layers anti-parallel from (antiparallel) through rubbing against one another and cause the edge orientation of the vertical plane of liquid crystal molecule.

By the UVA photoirradiation scheduled time with some strength, apply voltage (being generally 10V ~ 30V alternating-current, 1kHz) to indicating meter simultaneously and polymerizable compound is polymerized in indicating meter or testing cassete.In embodiment, if without illustrating on the contrary, adopt metal halide lamp and 100mW/cm ²intensity be polymerized.Use standard UV A gauge (there is the Hoenle UV-meter high end of UVA sensor) measured intensity.

Pitch angle is determined by Crystal Rotation test (Autronic Melchers TBA-105).Little value (namely relative to large the departing from 90 ° of angles) corresponds to large inclination at this.

VHR value is according to measuring as follows: the polymerisable monomer compound of 0.3% is added liquid crystal host mixture, and the mixture obtained to be introduced in VA-VHR testing cassete (do not rub, VA-polyimide alignment layer, thickness of liquid crystal layer d ≈ 6 μm).At 1V, 60Hz, under 64 μ s pulses, before and after UV exposure, at 100 DEG C, after 5 minutes, measure HR value (surveying instrument: Autronic-Melchers VHRM-105).

a) LC body mixture

comparative example C1

Nematic LC body mixture C1 is according to following preparation.

Mixture C 1 is not containing alkenyl compound.

embodiment 1

Nematic LC body mixture N1 is according to following preparation.

Mixture N1 contains alkenyl compound CC-3-V.

embodiment 2

Nematic LC body mixture N2 is according to following preparation.

Mixture N2 contains alkenyl compound CC-3-V and CC-3-V1.

embodiment 3

Nematic LC body mixture N3 is according to following preparation.

Mixture N3 contains alkenyl compound CC-3-V and CC-3-V1.

embodiment 4

Nematic LC body mixture N4 is according to following preparation.

Mixture N4 contains alkenyl compound CC-3-V.

embodiment 5

Nematic LC body mixture N5 is according to following preparation.

Mixture N5 contains alkenyl compound CC-3-V and CC-3-V1.

b) polymerizable mixture

Polymerizable mixture is in each case by adding monomer shown in table 2 to prepare in one of LC body mixture of Embodiment C 1 and embodiment 1-5 with the concentration of 0.3wt% respectively.The structure of monomer is shown in Table 1.

table 1

RM1 to RM6 represents three reactive monomers according to formula I of the present invention, and it is three reactive and containing at least one spacer groups, and CRM1 represents that the contrast monomer of double reactive and CRM2 represent that three is reactive but do not comprise the contrast monomer of spacer groups.

The title of each polymerizable mixture and composition are shown in following table 2.

table 2

P11-P56 is according to polymerizable mixture of the present invention, the polymerizable compound of its contained I and alkenyl compound.

CP11-CP16 is polymerizable compound containing formula I but does not comprise the control mixture of alkenyl compound.

CC11-CP52 is containing alkenyl compound but the control mixture of the polymerizable compound of not contained I

CC11 and CC12 is the control mixture that the polymerizable compound of neither contained I does not comprise alkenyl compound yet.

c) purposes embodiment

Each polymerizable mixture is inserted into (antiparallel friction, VA-polyimide alignment layer, the thickness d ≈ of LC layer 4 μm) in VA e/o testing cassete.With having 100mW/cm ²the time that the UV rayed testing cassete of intensity is specified, and apply 24V _rmsvoltage (alternating-current), this causes polymerisable monomer compound polymerization.

The VHR value of polymerizable mixture before and after exposing according to the UV of measurement described above.Result is shown in table 3-8, and wherein " day optical tests " represents the lower UV intensity of use but the irradiating step of time shutter longer than UV step.

table 3

Table 3 shows the VHR of the polymerizable control mixture based on the LC body mixture C1 without thiazolinyl.After 2 hours of daylight tests, polymerizable mixture CP11-13 with CP15 has similar VHR to polymerizable mixture CC11 with CC12.

table 4

Table 4 shows the VHR of the polymerizable mixture based on the LC body mixture N1 containing thiazolinyl.Polymerizable mixture P11-P13 according to the present invention has the highest VHR after UV and day optical tests, then be according to polymerizable mixture P15 of the present invention, not containing the polymerizable control mixture C12 of the polymerizable compound of formula I, and show Schwellenwert containing the polymerizable control mixture C11 of double reactive polymerizable compound.

table 5

Table 5 shows the VHR based on the polymerizable mixture comprising thiazolinyl LC body mixture N2.Containing the polymerizable compound of formula I polymerizable mixture P21-23 after uv exposure, with not containing formula I polymerizable compound polymerizable mixture C21 compared with.Compared with C21, have very high and stable VHR value after other day optical tests, for polymerizable mixture P21-23, VHR value is still higher.

table 6

Table 6 shows the VHR based on the polymerizable mixture comprising thiazolinyl LC body mixture N3.After UV exposure and day optical tests, polymerizable mixture P31 and P32 containing the polymerizable compound of formula I has higher VHR than the polymerizable mixture C31 of the polymerizable compound not containing formula I again.

table 7

Table 7 shows the VHR based on the polymerizable mixture comprising thiazolinyl LC body mixture N4.After uv exposure, polymerizable mixture P41 and P42 containing the polymerizable compound of formula I has higher VHR than the polymerizable control mixture C41 of the polymerizable compound not containing formula I again.

table 8

Table 8 shows the VHR based on the polymerizable mixture comprising thiazolinyl LC body mixture N5.After uv exposure, polymerizable mixture P51 and P52 containing the polymerizable compound of formula I has higher VHR than the polymerizable control mixture C51 of the polymerizable compound not containing formula I again.

In order to measure rate of polymerization, after different exposure time, measured in testing cassete the residue content (by weight %) not being polymerized RM by HPLC.For this reason, each mixture in testing cassete is polymerized under the condition listed.Then MEK (methylethylketone) is used from testing cassete, to flush out mixture and measure.

After different exposure time, in mixture, the residual concentration of each monomer as shown in Tables 9 and 10.

table 9

Table 9 remains RM concentration after showing the polymerization based on the polymerizable control mixture of the LC body mixture C1 without thiazolinyl.Compared with having the CC11 of double reactive polymerizable compound CRM1, mixture C P11, CP12 and CC12 respectively with three reactive polymerizable compound RM1, RM2 and CRM2 have low residue RM concentration and display is polymerized faster.

table 10

Table 10 show based on comprise thiazolinyl LC body mixture N1 polymerizable mixture polymerization after residue RM concentration.Here have and according to mixture P11, P12 and P13 of three reactive polymerizable compound RM1, RM2 and RM3 of formula I of the present invention, there is low residue RM concentration and show fast polymerization.On the other hand, the polymerizable mixture C12 containing polymerizable compound CRM2 (its be equally three reactive but be not the compound of formula I) does not show improvement relative to the polymerizable mixture CC11 with double reactive polymerizable compound CRM1.

This shows, when for comprising in thiazolinyl LC body mixture, with be that three reactive but Compound C RM2 that are not formula I compare with double reactive Compound C RM1 equally, three reactive compounds RM1, RM2 and RM3 according to formula I demonstrate remarkable improvement.

After UV pre-irradiation, pitch angle is determined by Crystal Rotation experiment (Autronic-Melchers TBA-105).Pitch angle is shown in table 11 to 13.

table 11

Table 11 is presented at and produces pre-tilt angle based in the polymerizable mixture without thiazolinyl LC body mixture C1.

table 12

Table 12 is presented at and produces pre-tilt angle based in the polymerizable mixture comprising thiazolinyl LC body mixture N1.

table 13

Table 13 is presented at and produces pre-tilt angle based in the polymerizable mixture comprising thiazolinyl LC body mixture N5.

As can be seen from table 11-13, compared with producing with the pre-tilt angle in the polymerizable control mixture of polymerizable compound not containing formula I, have in the polymerizable mixture according to the polymerizable compound of formula I, pre-tilt angle produces at least similar or even stronger.In addition, in polymerizable mixture according to the present invention, pre-tilt angle produces than faster in polymerizable control mixture.

Claims

1. liquid crystal (LC) medium, it comprises the polymerizable compound of one or more following formula I, and also comprises one or more mesomorphic comprising thiazolinyl or liquid crystalline cpds,

Wherein each group has following meanings

M is 0 or 1,

P ¹, P ², P ³represent polymerizable groups independently of one another,

R is 0,1,2 or 3,

R ^xrepresent P-Sp-, H, halogen, has the alkyl of the straight chain of 1 to 25 C atom, side chain or ring-type, wherein one or more non-conterminous CH ₂-group optionally to be replaced in the not direct interconnective mode of O-and/or S-atom by-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-and wherein one or more H atom are optionally replaced by F, Cl or P-Sp-, the aryl with 5 to 20 annular atomses of optional replacement, aryloxy, heteroaryl or heteroaryloxy

P has for P ¹one of implication provided,

Sp has for Sp ¹or Sp ²one of implication provided.

2. LC medium according to claim 1, wherein in the compound of formula I, P, P ¹, P ², P ³be selected from acrylate-based, methacrylate based and oxetanyl.

3. LC medium according to claim 1 and 2, wherein in the compound of formula I, is not those groups Sp of singly-bound ¹, Sp ²and Sp ³be selected from *-(CH ₂) _p1-, *-(CH ₂) _p2-O-(CH ₂) _p3-, *-(CH ₂) _p2-S-(CH ₂) _p3-, *-(CH ₂) _p2-NH-(CH ₂) _p3-, *-(CH ₂) _p1-O-, *-(CH ₂) _p1-CO-, *-(CH ₂) _p1-CO-O-, *-(CH ₂) _p1-O-CO-and

Wherein asterisk (*) represents the connection with each polymerizable groups, and p1 is the integer of 1 to 12, and p2 and p3 is the integer of 1 to 6 independently of one another.

4. LC medium according to any one of claim 1 to 3, wherein in the compound of formula I, at least one phenyl ring is replaced by one or two fluorine atom.

5. LC medium according to any one of claim 1 to 4, the compound of its Chinese style I is selected from following minor:

Wherein P ¹, P ², P ³, Sp ¹, Sp ², Sp ³, L and r have the implication provided in claim 1,2 or 3.

6. LC medium according to any one of claim 1 to 5, the compound of its Chinese style I is selected from following minor:

Wherein P ¹, P ²and P ³have the implication provided in claim 1 or 2, identical or be differently-O-,-CO-O-,-O-CO-or singly-bound when X occurs at every turn, m and n is 0,1,2,3,4,5 or 6 independently of one another, and one of m and n is not 0.

7. LC medium according to any one of claim 1 to 6, it comprises:

-polymerizable components A), it comprises one or more polymerizable compounds, and wherein at least one is the compound according to any one of claim 1 to 6, and

-liquid crystal components B), it comprises one or more mesomorphic comprising thiazolinyl or liquid crystalline cpds.

8. LC medium according to claim 7, in the mesomorphic wherein comprising thiazolinyl described or liquid crystalline cpd, described thiazolinyl is selected from the straight-chain alkenyl and cyclohexenyl with 2 to 7 C atoms, particularly vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, 1,4-tetrahydrobenzene-1-base and Isosorbide-5-Nitrae-tetrahydrobenzene-3-base.

9. LC medium according to claim 8 or claim 9, the concentration wherein comprising the compound of thiazolinyl described in B component is 5-100%.

10. LC medium according to any one of claim 1 to 9, wherein said comprise thiazolinyl mesomorphic or liquid crystal media be selected from following formula:

Identical or differently independently of one another there is following meanings when wherein each group occurs at every turn:

R ¹¹represent the thiazolinyl with 2 to 9 C atoms, if or at least one representative ring hexenyl of ring X, Y and Z, then also there is R ^done of implication,

R ¹²represent the alkyl with 1 to 12 C atom, in addition, wherein one or two non-conterminous CH ₂group can be replaced by the mode that-O-,-CH=CH-,-CO-,-OCO-or-COO-directly do not connect each other with O Sauerstoffatom,

Z ^xexpression-CH ₂cH ₂-,-CH=CH-,-CF ₂o-,-OCF ₂-,-CH ₂o-,-OCH ₂-,-CO-O-,-O-CO-,-C ₂f ₄-,-CF=CF-,-CH=CH-CH ₂o-or singly-bound, preferred singly-bound,

L ^1-4representing separately is H, F, Cl, OCF independently of one another ₃, CF ₃, CH ₃, CH ₂f or CHF ₂h, preferred H, F or Cl,

X represents 1 or 2,

Z represents 0 or 1.

11. LC media according to any one of claim 1 to 10, wherein said comprise thiazolinyl mesomorphic or liquid crystalline cpd be selected from following formula:

Wherein alkyl represents the straight chained alkyl with 1-6 C atom, and alkenyl and alkenyl* represents the straight-chain alkenyl with 2-7 C atom separately independently of one another, alkenyl and alkenyl* preferably represents CH ₂=CH-, CH ₂=CHCH ₂cH ₂-, CH ₃-CH=CH-, CH ₃-CH ₂-CH=CH-, CH ₃-(CH ₂) ₂-CH=CH-, CH ₃-(CH ₂) ₃-CH=CH-or CH ₃-CH=CH-(CH ₂) ₂-.

12. LC media according to any one of 1 to 11, wherein said comprise thiazolinyl mesomorphic or liquid crystalline cpd be selected from following formula:

13. LC media according to any one of claim 1 to 12, wherein said comprise thiazolinyl mesomorphic or liquid crystalline cpd be selected from following formula:

14. LC media according to any one of claim 1 to 13, wherein said comprise thiazolinyl mesomorphic or liquid crystalline cpd be selected from following formula:

15. LC media according to any one of claim 1 to 14, comprise the compound of one or more formula CY and/or PY:

Wherein each group has following implication:

A represents 1 or 2,

B represents 0 or 1,

represent

R ¹and R ²represent the alkyl with 1 to 12 C atom separately independently of one another, in addition, wherein one or two non-conterminous CH ₂group can be replaced in the not direct interconnective mode of O atom by-O-,-CH=CH-,-CO-,-O-CO-or-CO-O-,

Z ^xrepresent-CH=CH-,-CH ₂o-,-OCH ₂-,-CF ₂o-,-OCF ₂-,-O-,-CH ₂-,-CH ₂cH ₂-or singly-bound, be preferably singly-bound,

L ^1-4represent F, Cl, OCF independently of one another separately ₃, CF ₃, CH ₃, CH ₂f, CHF ₂.

16. LC media according to any one of claim 1 to 15, it comprises one or more following formula: compounds:

Wherein each group has following implication:

represent

Z ^yexpression-CH ₂cH ₂-,-CH=CH-,-CF ₂o-,-OCF ₂-,-CH ₂o-,-OCH ₂-,-COO-,-OCO-,-C ₂f ₄-,-CF=CF-or singly-bound.

17. LC media described in any one of claim 1 to 16, is characterized in that it contains the chiral dopant that at least one is selected from 120-121 page table B.

18. LC media described in any one of claim 1 to 17, is characterized in that it contains the stablizer that at least one is selected from 121-125 page table C.

19. LC media described in any one of claim 1 to 18, is characterized in that described polymerizable compound is through polymerization.

20. any one of claim 1 to 19 LC medium be used for LC indicating meter, be preferred for the purposes in the LC indicating meter of polymer-stabilized alignment (PSA) type.

21.LC indicating meter, it comprises the LC medium any one of claim 1 to 19.

22. LC indicating meters according to claim 21, it is the indicating meter of PSA type.

23. LC indicating meters according to claim 22, it is PSA-VA, PSA-OCB, PSA-IPS, PS-FFS, PSA-positivity-VA or PSA-TN indicating meter.

24. according to the described LC indicating meter of claim 22 or 23, it is characterized in that it comprises and has two substrates, two electrodes and substrate between the LC box of LC medium layer, wherein at least one substrate is printing opacity and at least one substrate has one or two electrode, described LC medium comprise through polymerization component and lower-molecular-weight component, the wherein said component through polymerization is by the polymerization acquisition in LC medium between the substrate of LC box of one or more polymerizable compounds, preferably when being polymerized to during electrode application voltage, wherein said LC medium is the LC medium any one of claim 1 to 19.

The method of the LC indicating meter of 25. manufactures any one of claim 22 to 24, it comprises the following steps: by the LC Filled Dielectrics any one of claim 1 to 18 in the LC box described in context with two substrates and two electrodes, and preferably when to electrode application voltage, be polymerized described polymerizable compound.

The method of the LC medium of 26. preparations any one of claim 1 to 18, it comprises the following steps: by one or more not polymerisable mesomorphic or liquid crystalline cpd, or the liquid crystal components B to limit as claim 7), the polymerizable compound limited any one of claim 1 to 6 with one or more and optionally mixing with other liquid crystalline cpds and/or additive.